Ch 05 MATLAB Applications in Chemical Engineering_陳奇中教授教學投影片
國 科 會 自 然 處 化學研究推動中心通訊 · 陳振中教授 NMR Associate Professor,...
Transcript of 國 科 會 自 然 處 化學研究推動中心通訊 · 陳振中教授 NMR Associate Professor,...
國 科 會 自 然 處 化學研究推動中心通訊
第 九十一 期
九十五年七月
目 錄
年度報告 ---------------------------------------------- 1
最新消息 ---------------------------------------------- 7
研討會報告 ------------------------------------------ 10
訪問教授報告 --------------------------------------- 26
九 十 四 年 度 工 作 報 告 ( 9 4 年 1 月 1 日 至 9 5 年 6 月 3 0 日 )
一 研 討 會
說 研 討 會 名 稱時 間主 辦 單 位參 加
人 數
主 持 人
1化學學門專題研究計劃申請
及審核座談會
94916 化學中心 33 劉緒宗教授
22005 台灣生物無機化學研討
會
94107-8 高雄醫學大學醫藥暨
應用化學系
156 王雲銘教授
3第八屆亞洲分析化學會議
941016-20 台灣大學化學系 380 林敬二教授
4第八屆亞洲分析化學會議會
前會
941015 淡江大學化學系 174 林孟山教授
5第八屆亞洲分析化學會議會
後會
9410 靜宜大學應化系 165 蔡素珍教授
6有機電激發材料第四屆產學
聯盟國際研討會 941125-26 中研院化學所 330 陶雨台教授
72006 國科會分析小組研討會 95225 靜宜應化系 150 蔡素珍教授
8無機錯鹽化學小組研討會 95428 中山大學化學系 165 梁蘭昌教授
92006 年台澳綠色化學研討會 9536 清華大學化學系 凌永健教授
10台灣國際化學研討會會後會941028-30 清華大學化學系 400 劉行讓教授
劉瑞雄教授
11台灣國際化學研討會會後會941031 中研院化學所 120 呂光烈教授
12結晶學小組研討會 94123 中研院生化所 50 蕭傳鐙博士
13奈米化學研討會 9515 台灣大學化學系 100 彭旭明教授
14Frontier Researches on
Chemical Science 95120-21 台灣大學化學系 120 汪根欉教授
15第十二屆分析化學技術交流
研討會
95520 高雄師範大學化學系 220 楊慶成教授
16第二十四屆台灣區觸媒與反
工程研討會
95623 中興大學化工系 120
17台灣質譜學會學術研討會 95 中山大學化學系 250 謝建台教授
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二中心訪問教授
姓名來訪日期及連絡人 主要專長 現職 1 Gary W Brudvig 94101-14 俞聖法博士
生物無機 Prof Yale University USA
2G M Hieftje 941015-22 林金全教授
原子分析光譜 儀器分析 感應器
Prof Indiana University USA
3Paul R Haddad 941016-23
林敬二教授
Liquid Chromatography Capillary Electrophoresis Ion Chromatography
Prof Univ of Tasmania Australian
4Eric Bakker 941014-20
林孟山教授
Potentiometry at Trace Levels Amperometric Ion Sensors
Prof Auburn University USA
5Alois FŰRSTNER 941028-31 劉行讓教授
Carbohydrate Chemistry Organic Synthesis Organometallic Chemistry
Prof the University of Dortmund Germany
6Michael J Krisch 941026-31
劉行讓教授
Organic Synthesis Organometallic Chemistry Catalysis
Prof University of Texas at Austin USA
7Frederick G West 941028-31 劉行讓教授
Synthetic Organic Chemistry Natural Products Chemistry Medicinal Chemistry
Prof University of Alberta Canada
8G Pattenden 941028-31 劉行讓教授
Synthetic Organic Natural Products ChemistryMedicinal Chemistry
Prof University of Nottingham United Kingdom
9A Ajayaghosh 94116-12 汪根欉教授
高分子超分子化學 印度國家科學工業研究委員會
研究員
10Charles P Casey 941118-26 江旭禎教授
生物有機化學 Prof Univ of Wisconsin-Madison USA
11 Andrew B Holmes 941123-26 陶雨台教授
Bioorganic Chemistry Polymeric Organic Materials Anticancer agents
Prof Melbourne University Australia
12 John P Fackler Jr 95320-326 劉鎮維教授
Inorganic Chemistry Professor Texas AampM Univ USA
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姓名來訪日期及連絡人 主要專長 現職 13Robert P Lemieux
95115-121
陳建添教授
有機材料液晶光學開關 Professor Queenrsquos Univ Kingston Canada
14Wayne L Gladfelter 95226-34 吉凱明教授
Organometallic and Inorganic Synthesis Nanocrystalspf solid state materials Ceramic Material Chemistry
Professor amp Chair Univ of Minnesota USA
15Charles G Riordan 95319-325
廖文峰教授
Bioinorganic Chemistry Professor amp Chair Univ of Delaware USA
16 Kazuhiko Nakatani 9535-311
張一知教授
生化有機DNA 定位選擇性斷
序DNA 定位選擇性鍵結
Prof The Institute of Scientific and Industrial Res Osaka Univ Japan
17 Jean-Jacques Girerd 951-5 月(未定) 彭旭明教授
生物無機化學磁性化學 Prof amp Director Univ Paris-sud France
18 Jan-Erling Baumlckvall 95312-318 陸天堯教授
Organic Chemistry 結合有機金屬化學及酵素催
化反應的先驅者
Prof Stockholms Univ Sweden
19 Axel G Griesbeck 953 28-42
楊吉水教授
有機光化學 有機化學
ProfUniversity of Cologne Germany
20 Hellmut Eckert 95223-227 陳振中教授
Solid state nuclear magnetic resonance spectroscopy techniques
Prof University of Muenster Germany
21 Martin Quack 953 14-320
李遠鵬教授
Molecular Kinetics and Spectroscopy
ETH Zuumlrich Labortorium fuumlr Physikalische chemie ETH Switzerland
22 Andre Ayral 9558-514 趙桂蓉教授
膠體化學無機薄膜及材料 Prof University Montpellier II France
23Johannes G Vos 9562-610 季昀教授
無機化學有機金屬 Professor School of Chemical Sciences Dublin City Univ Germany
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三國科會短期訪問教授審查
姓名來訪日期及連絡人 主 要 專 長 現 職 1Ziling(Ben) Xue 941028-31 劉瑞雄教授
Synthetic and Mechanistic Orgaometallic Inorganic Chemistry
Prof University of Tennessee USA
2SonBinh T Nguyen 941028-31 劉瑞雄教授
Catalysis Materials Chemistry PohotchemistryPhotocatalysis
Prof Northwestern University USA
3Omar M Yaghi 941028-31 劉瑞雄教授
Low density solids Hierarchical structures Smart crystalline sponges
Prof University of Michigan USA
4Kiyokatsu Jinno 941014-20 林敬二教授
High performance Liquid Chromatography Capillary Electrophoresis
Prof Toyohashi Univ of Technology Japan
5Shigeru Terabe 941016-23
林敬二教授
Capillary Electrophoresis Capillary Electrochromatography
Prof Univ of Hyogo Japan
6 Silvio Aime 94103-10 王雲銘教授
生物無機 Prof I F M University Italy
7 Teizo Kitagawa 94103-10 洪政雄教授
生物無機 Prof National Institutes of Natural Sciences Japan
8 Tetsuro Majima 941121-27 陳建添教授
Photochemistry Radiation Chemistry Nanoscience
Prof Osaka University Japan
9Jung-Il Jin 941123-27 陶雨台教授
光電材料 Prof Korea University Korea
10Chihaya Adachi 941123-27 陶雨台教授
光電材料 Prof Chitose Institute of Science and Technology Japan
11Robert Glaum 94913-916 王素蘭教授
無機固態化學 德國波昂大學教授
12Ramamoorthy A 94817-20 陳振中教授
NMR Associate Professor Univ of Michigan (Ann Arbor) USA
13 莊自強 941018-19 葉瑞銘教授
Polymer science Catalysis Functional materials
Prof The Penns Sate Univ USA
14 剛本正己
941018-19 葉瑞銘教授
Polymer Physics Polymer Eng Biomaterials
Associate Prof Toyota Technological Institute Japan
15 魏建謨 941120-23 葉華光教授
物理化學及放射化學 Prof Univ of Idaho USA
- 4 -
姓名來訪日期及連絡人 主 要 專 長 現 職
16Todd L Lowary 95430-56 劉行讓教授
Chemistry Glycobiology
Associate Prof The Univ of Alberta Canada
17Kwan Soo Kim 95212-218 洪上程教授
Organic synthesis Carbohydrate Chemistry
Professor Yonsei Univ Korea
18F Dean Toste 95423-429 陳建添教授
有機金屬催化 Assistant Prof Univ of California Berkeley USA
19 Mikio Takano 95320-325 劉如熹教授
Solid State Chemistry Prof Kyoto Univ Japan
20 Norio Miyaura 95430-56 陸天堯教授
有機合成化學 有機金屬化學
日本北海大學教授
21 Kazuko Matsumoto 941119-1124 劉陵崗教授
Chemistry 日本早稻田大學教授
22 Mitsuo Kira 95416-422 蘇明德教授
無機化學 合成化學
日本東北大學教授
23 Jacquelyn Gervay Hague 95310-315 林俊宏教授
Carbohydrate Chemistry Prof University of California Davis USA
24 David W C MacMillan 95310-316 劉陵崗教授
Organic Chemistry Prof The California Institute of Technology California USA
25Paul Jean Amoureux 941220-1227 丁尚武教授
Physics Electronics
Prof Lille-1 University France
26 Janet L Scott 95313-319 凌永健教授
有機合成 Prof Monash Univ Australia
27 Chris Strauss 953 13-319 凌永健教授
有機合成 Prof Monash Univ Australia
28 Milton Hearn 953 13-319 凌永健教授
分析化學 Prof Monash Univ Australia
29Takashi Ooi 95314-318 劉瑞雄教授
Organic Synthesis 日本京都大學副教授
- 5 -
姓名來訪日期及連絡人 主 要 專 長 現 職
30Nicholas Andrew Morrice 95312-321 陳淑慧教授
蛋白質體分析 Head of Proteomics NRC Research Support Scientist Univ of Dundee UK
31A J Arduengo III 95910-917 林志彪教授
Organic Chemistry Inorganic Chemistry
Professor Department of Chemistry The Univ of Alabama
32Kei Takeda 9564-610 王英基教授
Invention of new reactions Their mechanistic studies and synthetic applications
日本廣島大學教授
33裴堅(大陸科技人士) 95213-217 陸天堯教授
有機合成有機材料化學 北京大學化學學院教授
34Shiou-Jyh Hwu 9543-47 王素蘭教授
Solid State Chemistry Professor Clemson Univ USA
35陳守信教授 95516-525 林滄浪教授
X-ray and Neutron Scattering spectroscopy of Complex Fluids and Soft Matter
Professor Massachusetts Institute of Technology USA
36錢明仁教授 95514-67 陳貴賢教授
電化學 Professor University of North Texas USA
四國際研討會及兩岸研討會之審查
研 討 會 名 稱 申請人及單位 建議補助金額
1第十六屆國際磁共振學會研討會 中研院生醫所黃太煌教授 150萬至200萬元之間
2化學動態學新趨勢 中研院原分所劉國平教授 120 萬元
3第十屆東亞化學反應研討會 中研院原分所張煥正教授 20 萬元
42005 年第 1 屆台越理論計算化學研討會 交通大學林明璋教授 10 萬元
5第八屆亞洲結晶學國際研討會 清華大學理學院張石麟院長120 萬元
6 2006 年台灣生物無機研討會 中研院化學所洪政雄教授 56 萬元
- 6 -
最 新 消 息
第 192 次(95629)中心審議會決議
(一) 同意推薦下列十四位教授為中心訪問教授生活費補助以不超過七天為限並須
給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Jean-Pascal Sutter
95101-109 鄭建中教授
Nano-porous architectures Molecule-based magnets Nano-magnets
法國Toulous(土魯士)國家化學研究院資深
研究員
補助教授級生活
費及機票費
2 Junji Inanaga 951018-1024 方俊民教授
鑭系金屬有機化學不
對稱及官能性有機合成
日本九州大學教授 補助教授級生活
費及機票費
3 Donald H Levy 951210-1216 劉國平教授
Laser spectroscopy in supersonic molecular beams
Professor the University of Chicago USA
補助院士級生活
費及機票費
4 Henry Shaefer 951210-1216 劉國平教授
理論化學 Professor the University of Georgia USA
補助院士級生活
費及機票費
5 John C Tully 951210-1216 劉國平教授
理論發展分子動力學 Professor Yale University USA
補助院士級生活
費及機票費
6 Thomas T Tidwell 951024-1030 宋光生教授
Destabilized carbocations Ketene chemistry Aromaticity and Antiaromaticity
Professor Univ of Toronto Canada President of Canadian Chemical Society
1補助教授級生
活費及機票費
2請安排與中國
化學會會長見
面並在台北地
區增加一場演
講 7 John Ewart McGrady 9511 金必耀教授
量子化學計算化學 Professor of Computational Chemistry Univ of Glasgow UK
補助教授級生活
費及機票費
8 Hisao Nishiyama 95911-917 鄭建鴻教授
不對稱催化反應有機
合成 日本名古屋大學教授 補助教授級生活
費及機票費
9 Martin Head-Gordon 95129-1219 許昭萍博士
Theoretical Chemistry Electronic Structure Calculations
Professor Univ of California(Berkeley) USA
補助教授級生活
費及機票費
10 Masakatsu Shibasaki 951123-1129 王伯昌教授
生物有機有機合成
藥物化學 Professor The University of Tokyo Japan
補助教授級生活
費及機票費
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姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 11 Daniel G Nocera
951123-1129 王伯昌教授
奈米材料能源開發
電子轉移 Professor Massachusetts Institute of Technology USA
補助教授級生活
費及機票費
12Koichi Ohno 951121-26 游靜惠教授
Theoretical Chemistry Professor Tohoku University Japan
補助教授級生活
費及機票費
13Satoshi Yabushita 951121-26 游靜惠教授
Theoretical Chemistry Professor Keio University Japan
補助教授級生活
費及機票費
14 Laren M Tolbert 951119-26 陳建添教授
Organic photochemistryPhotobiology Electronic materials
Professor Associate Editor for the Journal of the American Chemical Society
補助教授級生活
費及機票費
(二) 同意推薦下列十位教授為國科會國際科技人士短期訪問教授生活費補助以不超
過七天為限並須給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Ann Mary Chippindale
95101-108 王素蘭教授
Solid State Chemistry Professor The University of Reading UK
補助教授級生活費及機票費
2 Steven Chu 951210-1216 倪其焜博士
物理應用物理 諾貝爾得主 Director Lawrence Berkeley National Laboratory USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 3 F Sherwood Rowland
951210-1216 倪其焜博士
Atmospheric Chemistry Chemical Kinetics
諾貝爾得主 Professor University of California Irvine USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶機票費
4 Dudley R Herschbach 951210-1216 倪其焜博士
Chemical Physics 諾貝爾得主 Professor Harvard University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 5J ohn B Fenn
951210-1216 倪其焜博士
Analytical chemistry 諾貝爾得主 Professor Virginia Commonwealth University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費
- 8 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 6 John C Polanyi
951210-1216 倪其焜博士
物理化學 諾貝爾得主 Professor Toronto University Canada
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 7 Chul-Ho Jun 951021-1027 鄭建鴻教授
催化反應金屬有機綠色化學
Professor Yonsei University Korea
補助教授級生活費及機票費
8 Nakeheol Jeong 951016-1021 陳竹亭教授
Organic Chemistry Professor Korea University Korea
補助教授級生活費及機票費
9 Hiroyuki Isobe 95111-116 陳竹亭教授
Organic Chemistry Associate Professor The University of Tokyo Japan
補助教授級生活費及機票費
10 Peter H Seeberger 95118-1113 洪上程教授
Organic Synthesis Carbohydrate Chemistry
Professor Eidgenossische Technische Hochschule Zurich Germany
補助教授級生活費及機票費
(三) 同意推薦下列研討會為國科會國際研討會
會 議 名 稱 建 議 補 助 經 費 備 註
1第八屆亞洲結晶學國際研討會 1200000 元
2 2006 年台灣生物無機研討會 560000 元
(四) 同意補助下列研討會經費如下
會 議 名 稱 補助金額 備 註
理論與計算化學研討會 49000 元 請檢據實報實銷
- 9 -
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
目 錄
年度報告 ---------------------------------------------- 1
最新消息 ---------------------------------------------- 7
研討會報告 ------------------------------------------ 10
訪問教授報告 --------------------------------------- 26
九 十 四 年 度 工 作 報 告 ( 9 4 年 1 月 1 日 至 9 5 年 6 月 3 0 日 )
一 研 討 會
說 研 討 會 名 稱時 間主 辦 單 位參 加
人 數
主 持 人
1化學學門專題研究計劃申請
及審核座談會
94916 化學中心 33 劉緒宗教授
22005 台灣生物無機化學研討
會
94107-8 高雄醫學大學醫藥暨
應用化學系
156 王雲銘教授
3第八屆亞洲分析化學會議
941016-20 台灣大學化學系 380 林敬二教授
4第八屆亞洲分析化學會議會
前會
941015 淡江大學化學系 174 林孟山教授
5第八屆亞洲分析化學會議會
後會
9410 靜宜大學應化系 165 蔡素珍教授
6有機電激發材料第四屆產學
聯盟國際研討會 941125-26 中研院化學所 330 陶雨台教授
72006 國科會分析小組研討會 95225 靜宜應化系 150 蔡素珍教授
8無機錯鹽化學小組研討會 95428 中山大學化學系 165 梁蘭昌教授
92006 年台澳綠色化學研討會 9536 清華大學化學系 凌永健教授
10台灣國際化學研討會會後會941028-30 清華大學化學系 400 劉行讓教授
劉瑞雄教授
11台灣國際化學研討會會後會941031 中研院化學所 120 呂光烈教授
12結晶學小組研討會 94123 中研院生化所 50 蕭傳鐙博士
13奈米化學研討會 9515 台灣大學化學系 100 彭旭明教授
14Frontier Researches on
Chemical Science 95120-21 台灣大學化學系 120 汪根欉教授
15第十二屆分析化學技術交流
研討會
95520 高雄師範大學化學系 220 楊慶成教授
16第二十四屆台灣區觸媒與反
工程研討會
95623 中興大學化工系 120
17台灣質譜學會學術研討會 95 中山大學化學系 250 謝建台教授
- 1 -
二中心訪問教授
姓名來訪日期及連絡人 主要專長 現職 1 Gary W Brudvig 94101-14 俞聖法博士
生物無機 Prof Yale University USA
2G M Hieftje 941015-22 林金全教授
原子分析光譜 儀器分析 感應器
Prof Indiana University USA
3Paul R Haddad 941016-23
林敬二教授
Liquid Chromatography Capillary Electrophoresis Ion Chromatography
Prof Univ of Tasmania Australian
4Eric Bakker 941014-20
林孟山教授
Potentiometry at Trace Levels Amperometric Ion Sensors
Prof Auburn University USA
5Alois FŰRSTNER 941028-31 劉行讓教授
Carbohydrate Chemistry Organic Synthesis Organometallic Chemistry
Prof the University of Dortmund Germany
6Michael J Krisch 941026-31
劉行讓教授
Organic Synthesis Organometallic Chemistry Catalysis
Prof University of Texas at Austin USA
7Frederick G West 941028-31 劉行讓教授
Synthetic Organic Chemistry Natural Products Chemistry Medicinal Chemistry
Prof University of Alberta Canada
8G Pattenden 941028-31 劉行讓教授
Synthetic Organic Natural Products ChemistryMedicinal Chemistry
Prof University of Nottingham United Kingdom
9A Ajayaghosh 94116-12 汪根欉教授
高分子超分子化學 印度國家科學工業研究委員會
研究員
10Charles P Casey 941118-26 江旭禎教授
生物有機化學 Prof Univ of Wisconsin-Madison USA
11 Andrew B Holmes 941123-26 陶雨台教授
Bioorganic Chemistry Polymeric Organic Materials Anticancer agents
Prof Melbourne University Australia
12 John P Fackler Jr 95320-326 劉鎮維教授
Inorganic Chemistry Professor Texas AampM Univ USA
- 2 -
姓名來訪日期及連絡人 主要專長 現職 13Robert P Lemieux
95115-121
陳建添教授
有機材料液晶光學開關 Professor Queenrsquos Univ Kingston Canada
14Wayne L Gladfelter 95226-34 吉凱明教授
Organometallic and Inorganic Synthesis Nanocrystalspf solid state materials Ceramic Material Chemistry
Professor amp Chair Univ of Minnesota USA
15Charles G Riordan 95319-325
廖文峰教授
Bioinorganic Chemistry Professor amp Chair Univ of Delaware USA
16 Kazuhiko Nakatani 9535-311
張一知教授
生化有機DNA 定位選擇性斷
序DNA 定位選擇性鍵結
Prof The Institute of Scientific and Industrial Res Osaka Univ Japan
17 Jean-Jacques Girerd 951-5 月(未定) 彭旭明教授
生物無機化學磁性化學 Prof amp Director Univ Paris-sud France
18 Jan-Erling Baumlckvall 95312-318 陸天堯教授
Organic Chemistry 結合有機金屬化學及酵素催
化反應的先驅者
Prof Stockholms Univ Sweden
19 Axel G Griesbeck 953 28-42
楊吉水教授
有機光化學 有機化學
ProfUniversity of Cologne Germany
20 Hellmut Eckert 95223-227 陳振中教授
Solid state nuclear magnetic resonance spectroscopy techniques
Prof University of Muenster Germany
21 Martin Quack 953 14-320
李遠鵬教授
Molecular Kinetics and Spectroscopy
ETH Zuumlrich Labortorium fuumlr Physikalische chemie ETH Switzerland
22 Andre Ayral 9558-514 趙桂蓉教授
膠體化學無機薄膜及材料 Prof University Montpellier II France
23Johannes G Vos 9562-610 季昀教授
無機化學有機金屬 Professor School of Chemical Sciences Dublin City Univ Germany
- 3 -
三國科會短期訪問教授審查
姓名來訪日期及連絡人 主 要 專 長 現 職 1Ziling(Ben) Xue 941028-31 劉瑞雄教授
Synthetic and Mechanistic Orgaometallic Inorganic Chemistry
Prof University of Tennessee USA
2SonBinh T Nguyen 941028-31 劉瑞雄教授
Catalysis Materials Chemistry PohotchemistryPhotocatalysis
Prof Northwestern University USA
3Omar M Yaghi 941028-31 劉瑞雄教授
Low density solids Hierarchical structures Smart crystalline sponges
Prof University of Michigan USA
4Kiyokatsu Jinno 941014-20 林敬二教授
High performance Liquid Chromatography Capillary Electrophoresis
Prof Toyohashi Univ of Technology Japan
5Shigeru Terabe 941016-23
林敬二教授
Capillary Electrophoresis Capillary Electrochromatography
Prof Univ of Hyogo Japan
6 Silvio Aime 94103-10 王雲銘教授
生物無機 Prof I F M University Italy
7 Teizo Kitagawa 94103-10 洪政雄教授
生物無機 Prof National Institutes of Natural Sciences Japan
8 Tetsuro Majima 941121-27 陳建添教授
Photochemistry Radiation Chemistry Nanoscience
Prof Osaka University Japan
9Jung-Il Jin 941123-27 陶雨台教授
光電材料 Prof Korea University Korea
10Chihaya Adachi 941123-27 陶雨台教授
光電材料 Prof Chitose Institute of Science and Technology Japan
11Robert Glaum 94913-916 王素蘭教授
無機固態化學 德國波昂大學教授
12Ramamoorthy A 94817-20 陳振中教授
NMR Associate Professor Univ of Michigan (Ann Arbor) USA
13 莊自強 941018-19 葉瑞銘教授
Polymer science Catalysis Functional materials
Prof The Penns Sate Univ USA
14 剛本正己
941018-19 葉瑞銘教授
Polymer Physics Polymer Eng Biomaterials
Associate Prof Toyota Technological Institute Japan
15 魏建謨 941120-23 葉華光教授
物理化學及放射化學 Prof Univ of Idaho USA
- 4 -
姓名來訪日期及連絡人 主 要 專 長 現 職
16Todd L Lowary 95430-56 劉行讓教授
Chemistry Glycobiology
Associate Prof The Univ of Alberta Canada
17Kwan Soo Kim 95212-218 洪上程教授
Organic synthesis Carbohydrate Chemistry
Professor Yonsei Univ Korea
18F Dean Toste 95423-429 陳建添教授
有機金屬催化 Assistant Prof Univ of California Berkeley USA
19 Mikio Takano 95320-325 劉如熹教授
Solid State Chemistry Prof Kyoto Univ Japan
20 Norio Miyaura 95430-56 陸天堯教授
有機合成化學 有機金屬化學
日本北海大學教授
21 Kazuko Matsumoto 941119-1124 劉陵崗教授
Chemistry 日本早稻田大學教授
22 Mitsuo Kira 95416-422 蘇明德教授
無機化學 合成化學
日本東北大學教授
23 Jacquelyn Gervay Hague 95310-315 林俊宏教授
Carbohydrate Chemistry Prof University of California Davis USA
24 David W C MacMillan 95310-316 劉陵崗教授
Organic Chemistry Prof The California Institute of Technology California USA
25Paul Jean Amoureux 941220-1227 丁尚武教授
Physics Electronics
Prof Lille-1 University France
26 Janet L Scott 95313-319 凌永健教授
有機合成 Prof Monash Univ Australia
27 Chris Strauss 953 13-319 凌永健教授
有機合成 Prof Monash Univ Australia
28 Milton Hearn 953 13-319 凌永健教授
分析化學 Prof Monash Univ Australia
29Takashi Ooi 95314-318 劉瑞雄教授
Organic Synthesis 日本京都大學副教授
- 5 -
姓名來訪日期及連絡人 主 要 專 長 現 職
30Nicholas Andrew Morrice 95312-321 陳淑慧教授
蛋白質體分析 Head of Proteomics NRC Research Support Scientist Univ of Dundee UK
31A J Arduengo III 95910-917 林志彪教授
Organic Chemistry Inorganic Chemistry
Professor Department of Chemistry The Univ of Alabama
32Kei Takeda 9564-610 王英基教授
Invention of new reactions Their mechanistic studies and synthetic applications
日本廣島大學教授
33裴堅(大陸科技人士) 95213-217 陸天堯教授
有機合成有機材料化學 北京大學化學學院教授
34Shiou-Jyh Hwu 9543-47 王素蘭教授
Solid State Chemistry Professor Clemson Univ USA
35陳守信教授 95516-525 林滄浪教授
X-ray and Neutron Scattering spectroscopy of Complex Fluids and Soft Matter
Professor Massachusetts Institute of Technology USA
36錢明仁教授 95514-67 陳貴賢教授
電化學 Professor University of North Texas USA
四國際研討會及兩岸研討會之審查
研 討 會 名 稱 申請人及單位 建議補助金額
1第十六屆國際磁共振學會研討會 中研院生醫所黃太煌教授 150萬至200萬元之間
2化學動態學新趨勢 中研院原分所劉國平教授 120 萬元
3第十屆東亞化學反應研討會 中研院原分所張煥正教授 20 萬元
42005 年第 1 屆台越理論計算化學研討會 交通大學林明璋教授 10 萬元
5第八屆亞洲結晶學國際研討會 清華大學理學院張石麟院長120 萬元
6 2006 年台灣生物無機研討會 中研院化學所洪政雄教授 56 萬元
- 6 -
最 新 消 息
第 192 次(95629)中心審議會決議
(一) 同意推薦下列十四位教授為中心訪問教授生活費補助以不超過七天為限並須
給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Jean-Pascal Sutter
95101-109 鄭建中教授
Nano-porous architectures Molecule-based magnets Nano-magnets
法國Toulous(土魯士)國家化學研究院資深
研究員
補助教授級生活
費及機票費
2 Junji Inanaga 951018-1024 方俊民教授
鑭系金屬有機化學不
對稱及官能性有機合成
日本九州大學教授 補助教授級生活
費及機票費
3 Donald H Levy 951210-1216 劉國平教授
Laser spectroscopy in supersonic molecular beams
Professor the University of Chicago USA
補助院士級生活
費及機票費
4 Henry Shaefer 951210-1216 劉國平教授
理論化學 Professor the University of Georgia USA
補助院士級生活
費及機票費
5 John C Tully 951210-1216 劉國平教授
理論發展分子動力學 Professor Yale University USA
補助院士級生活
費及機票費
6 Thomas T Tidwell 951024-1030 宋光生教授
Destabilized carbocations Ketene chemistry Aromaticity and Antiaromaticity
Professor Univ of Toronto Canada President of Canadian Chemical Society
1補助教授級生
活費及機票費
2請安排與中國
化學會會長見
面並在台北地
區增加一場演
講 7 John Ewart McGrady 9511 金必耀教授
量子化學計算化學 Professor of Computational Chemistry Univ of Glasgow UK
補助教授級生活
費及機票費
8 Hisao Nishiyama 95911-917 鄭建鴻教授
不對稱催化反應有機
合成 日本名古屋大學教授 補助教授級生活
費及機票費
9 Martin Head-Gordon 95129-1219 許昭萍博士
Theoretical Chemistry Electronic Structure Calculations
Professor Univ of California(Berkeley) USA
補助教授級生活
費及機票費
10 Masakatsu Shibasaki 951123-1129 王伯昌教授
生物有機有機合成
藥物化學 Professor The University of Tokyo Japan
補助教授級生活
費及機票費
- 7 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 11 Daniel G Nocera
951123-1129 王伯昌教授
奈米材料能源開發
電子轉移 Professor Massachusetts Institute of Technology USA
補助教授級生活
費及機票費
12Koichi Ohno 951121-26 游靜惠教授
Theoretical Chemistry Professor Tohoku University Japan
補助教授級生活
費及機票費
13Satoshi Yabushita 951121-26 游靜惠教授
Theoretical Chemistry Professor Keio University Japan
補助教授級生活
費及機票費
14 Laren M Tolbert 951119-26 陳建添教授
Organic photochemistryPhotobiology Electronic materials
Professor Associate Editor for the Journal of the American Chemical Society
補助教授級生活
費及機票費
(二) 同意推薦下列十位教授為國科會國際科技人士短期訪問教授生活費補助以不超
過七天為限並須給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Ann Mary Chippindale
95101-108 王素蘭教授
Solid State Chemistry Professor The University of Reading UK
補助教授級生活費及機票費
2 Steven Chu 951210-1216 倪其焜博士
物理應用物理 諾貝爾得主 Director Lawrence Berkeley National Laboratory USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 3 F Sherwood Rowland
951210-1216 倪其焜博士
Atmospheric Chemistry Chemical Kinetics
諾貝爾得主 Professor University of California Irvine USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶機票費
4 Dudley R Herschbach 951210-1216 倪其焜博士
Chemical Physics 諾貝爾得主 Professor Harvard University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 5J ohn B Fenn
951210-1216 倪其焜博士
Analytical chemistry 諾貝爾得主 Professor Virginia Commonwealth University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費
- 8 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 6 John C Polanyi
951210-1216 倪其焜博士
物理化學 諾貝爾得主 Professor Toronto University Canada
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 7 Chul-Ho Jun 951021-1027 鄭建鴻教授
催化反應金屬有機綠色化學
Professor Yonsei University Korea
補助教授級生活費及機票費
8 Nakeheol Jeong 951016-1021 陳竹亭教授
Organic Chemistry Professor Korea University Korea
補助教授級生活費及機票費
9 Hiroyuki Isobe 95111-116 陳竹亭教授
Organic Chemistry Associate Professor The University of Tokyo Japan
補助教授級生活費及機票費
10 Peter H Seeberger 95118-1113 洪上程教授
Organic Synthesis Carbohydrate Chemistry
Professor Eidgenossische Technische Hochschule Zurich Germany
補助教授級生活費及機票費
(三) 同意推薦下列研討會為國科會國際研討會
會 議 名 稱 建 議 補 助 經 費 備 註
1第八屆亞洲結晶學國際研討會 1200000 元
2 2006 年台灣生物無機研討會 560000 元
(四) 同意補助下列研討會經費如下
會 議 名 稱 補助金額 備 註
理論與計算化學研討會 49000 元 請檢據實報實銷
- 9 -
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
九 十 四 年 度 工 作 報 告 ( 9 4 年 1 月 1 日 至 9 5 年 6 月 3 0 日 )
一 研 討 會
說 研 討 會 名 稱時 間主 辦 單 位參 加
人 數
主 持 人
1化學學門專題研究計劃申請
及審核座談會
94916 化學中心 33 劉緒宗教授
22005 台灣生物無機化學研討
會
94107-8 高雄醫學大學醫藥暨
應用化學系
156 王雲銘教授
3第八屆亞洲分析化學會議
941016-20 台灣大學化學系 380 林敬二教授
4第八屆亞洲分析化學會議會
前會
941015 淡江大學化學系 174 林孟山教授
5第八屆亞洲分析化學會議會
後會
9410 靜宜大學應化系 165 蔡素珍教授
6有機電激發材料第四屆產學
聯盟國際研討會 941125-26 中研院化學所 330 陶雨台教授
72006 國科會分析小組研討會 95225 靜宜應化系 150 蔡素珍教授
8無機錯鹽化學小組研討會 95428 中山大學化學系 165 梁蘭昌教授
92006 年台澳綠色化學研討會 9536 清華大學化學系 凌永健教授
10台灣國際化學研討會會後會941028-30 清華大學化學系 400 劉行讓教授
劉瑞雄教授
11台灣國際化學研討會會後會941031 中研院化學所 120 呂光烈教授
12結晶學小組研討會 94123 中研院生化所 50 蕭傳鐙博士
13奈米化學研討會 9515 台灣大學化學系 100 彭旭明教授
14Frontier Researches on
Chemical Science 95120-21 台灣大學化學系 120 汪根欉教授
15第十二屆分析化學技術交流
研討會
95520 高雄師範大學化學系 220 楊慶成教授
16第二十四屆台灣區觸媒與反
工程研討會
95623 中興大學化工系 120
17台灣質譜學會學術研討會 95 中山大學化學系 250 謝建台教授
- 1 -
二中心訪問教授
姓名來訪日期及連絡人 主要專長 現職 1 Gary W Brudvig 94101-14 俞聖法博士
生物無機 Prof Yale University USA
2G M Hieftje 941015-22 林金全教授
原子分析光譜 儀器分析 感應器
Prof Indiana University USA
3Paul R Haddad 941016-23
林敬二教授
Liquid Chromatography Capillary Electrophoresis Ion Chromatography
Prof Univ of Tasmania Australian
4Eric Bakker 941014-20
林孟山教授
Potentiometry at Trace Levels Amperometric Ion Sensors
Prof Auburn University USA
5Alois FŰRSTNER 941028-31 劉行讓教授
Carbohydrate Chemistry Organic Synthesis Organometallic Chemistry
Prof the University of Dortmund Germany
6Michael J Krisch 941026-31
劉行讓教授
Organic Synthesis Organometallic Chemistry Catalysis
Prof University of Texas at Austin USA
7Frederick G West 941028-31 劉行讓教授
Synthetic Organic Chemistry Natural Products Chemistry Medicinal Chemistry
Prof University of Alberta Canada
8G Pattenden 941028-31 劉行讓教授
Synthetic Organic Natural Products ChemistryMedicinal Chemistry
Prof University of Nottingham United Kingdom
9A Ajayaghosh 94116-12 汪根欉教授
高分子超分子化學 印度國家科學工業研究委員會
研究員
10Charles P Casey 941118-26 江旭禎教授
生物有機化學 Prof Univ of Wisconsin-Madison USA
11 Andrew B Holmes 941123-26 陶雨台教授
Bioorganic Chemistry Polymeric Organic Materials Anticancer agents
Prof Melbourne University Australia
12 John P Fackler Jr 95320-326 劉鎮維教授
Inorganic Chemistry Professor Texas AampM Univ USA
- 2 -
姓名來訪日期及連絡人 主要專長 現職 13Robert P Lemieux
95115-121
陳建添教授
有機材料液晶光學開關 Professor Queenrsquos Univ Kingston Canada
14Wayne L Gladfelter 95226-34 吉凱明教授
Organometallic and Inorganic Synthesis Nanocrystalspf solid state materials Ceramic Material Chemistry
Professor amp Chair Univ of Minnesota USA
15Charles G Riordan 95319-325
廖文峰教授
Bioinorganic Chemistry Professor amp Chair Univ of Delaware USA
16 Kazuhiko Nakatani 9535-311
張一知教授
生化有機DNA 定位選擇性斷
序DNA 定位選擇性鍵結
Prof The Institute of Scientific and Industrial Res Osaka Univ Japan
17 Jean-Jacques Girerd 951-5 月(未定) 彭旭明教授
生物無機化學磁性化學 Prof amp Director Univ Paris-sud France
18 Jan-Erling Baumlckvall 95312-318 陸天堯教授
Organic Chemistry 結合有機金屬化學及酵素催
化反應的先驅者
Prof Stockholms Univ Sweden
19 Axel G Griesbeck 953 28-42
楊吉水教授
有機光化學 有機化學
ProfUniversity of Cologne Germany
20 Hellmut Eckert 95223-227 陳振中教授
Solid state nuclear magnetic resonance spectroscopy techniques
Prof University of Muenster Germany
21 Martin Quack 953 14-320
李遠鵬教授
Molecular Kinetics and Spectroscopy
ETH Zuumlrich Labortorium fuumlr Physikalische chemie ETH Switzerland
22 Andre Ayral 9558-514 趙桂蓉教授
膠體化學無機薄膜及材料 Prof University Montpellier II France
23Johannes G Vos 9562-610 季昀教授
無機化學有機金屬 Professor School of Chemical Sciences Dublin City Univ Germany
- 3 -
三國科會短期訪問教授審查
姓名來訪日期及連絡人 主 要 專 長 現 職 1Ziling(Ben) Xue 941028-31 劉瑞雄教授
Synthetic and Mechanistic Orgaometallic Inorganic Chemistry
Prof University of Tennessee USA
2SonBinh T Nguyen 941028-31 劉瑞雄教授
Catalysis Materials Chemistry PohotchemistryPhotocatalysis
Prof Northwestern University USA
3Omar M Yaghi 941028-31 劉瑞雄教授
Low density solids Hierarchical structures Smart crystalline sponges
Prof University of Michigan USA
4Kiyokatsu Jinno 941014-20 林敬二教授
High performance Liquid Chromatography Capillary Electrophoresis
Prof Toyohashi Univ of Technology Japan
5Shigeru Terabe 941016-23
林敬二教授
Capillary Electrophoresis Capillary Electrochromatography
Prof Univ of Hyogo Japan
6 Silvio Aime 94103-10 王雲銘教授
生物無機 Prof I F M University Italy
7 Teizo Kitagawa 94103-10 洪政雄教授
生物無機 Prof National Institutes of Natural Sciences Japan
8 Tetsuro Majima 941121-27 陳建添教授
Photochemistry Radiation Chemistry Nanoscience
Prof Osaka University Japan
9Jung-Il Jin 941123-27 陶雨台教授
光電材料 Prof Korea University Korea
10Chihaya Adachi 941123-27 陶雨台教授
光電材料 Prof Chitose Institute of Science and Technology Japan
11Robert Glaum 94913-916 王素蘭教授
無機固態化學 德國波昂大學教授
12Ramamoorthy A 94817-20 陳振中教授
NMR Associate Professor Univ of Michigan (Ann Arbor) USA
13 莊自強 941018-19 葉瑞銘教授
Polymer science Catalysis Functional materials
Prof The Penns Sate Univ USA
14 剛本正己
941018-19 葉瑞銘教授
Polymer Physics Polymer Eng Biomaterials
Associate Prof Toyota Technological Institute Japan
15 魏建謨 941120-23 葉華光教授
物理化學及放射化學 Prof Univ of Idaho USA
- 4 -
姓名來訪日期及連絡人 主 要 專 長 現 職
16Todd L Lowary 95430-56 劉行讓教授
Chemistry Glycobiology
Associate Prof The Univ of Alberta Canada
17Kwan Soo Kim 95212-218 洪上程教授
Organic synthesis Carbohydrate Chemistry
Professor Yonsei Univ Korea
18F Dean Toste 95423-429 陳建添教授
有機金屬催化 Assistant Prof Univ of California Berkeley USA
19 Mikio Takano 95320-325 劉如熹教授
Solid State Chemistry Prof Kyoto Univ Japan
20 Norio Miyaura 95430-56 陸天堯教授
有機合成化學 有機金屬化學
日本北海大學教授
21 Kazuko Matsumoto 941119-1124 劉陵崗教授
Chemistry 日本早稻田大學教授
22 Mitsuo Kira 95416-422 蘇明德教授
無機化學 合成化學
日本東北大學教授
23 Jacquelyn Gervay Hague 95310-315 林俊宏教授
Carbohydrate Chemistry Prof University of California Davis USA
24 David W C MacMillan 95310-316 劉陵崗教授
Organic Chemistry Prof The California Institute of Technology California USA
25Paul Jean Amoureux 941220-1227 丁尚武教授
Physics Electronics
Prof Lille-1 University France
26 Janet L Scott 95313-319 凌永健教授
有機合成 Prof Monash Univ Australia
27 Chris Strauss 953 13-319 凌永健教授
有機合成 Prof Monash Univ Australia
28 Milton Hearn 953 13-319 凌永健教授
分析化學 Prof Monash Univ Australia
29Takashi Ooi 95314-318 劉瑞雄教授
Organic Synthesis 日本京都大學副教授
- 5 -
姓名來訪日期及連絡人 主 要 專 長 現 職
30Nicholas Andrew Morrice 95312-321 陳淑慧教授
蛋白質體分析 Head of Proteomics NRC Research Support Scientist Univ of Dundee UK
31A J Arduengo III 95910-917 林志彪教授
Organic Chemistry Inorganic Chemistry
Professor Department of Chemistry The Univ of Alabama
32Kei Takeda 9564-610 王英基教授
Invention of new reactions Their mechanistic studies and synthetic applications
日本廣島大學教授
33裴堅(大陸科技人士) 95213-217 陸天堯教授
有機合成有機材料化學 北京大學化學學院教授
34Shiou-Jyh Hwu 9543-47 王素蘭教授
Solid State Chemistry Professor Clemson Univ USA
35陳守信教授 95516-525 林滄浪教授
X-ray and Neutron Scattering spectroscopy of Complex Fluids and Soft Matter
Professor Massachusetts Institute of Technology USA
36錢明仁教授 95514-67 陳貴賢教授
電化學 Professor University of North Texas USA
四國際研討會及兩岸研討會之審查
研 討 會 名 稱 申請人及單位 建議補助金額
1第十六屆國際磁共振學會研討會 中研院生醫所黃太煌教授 150萬至200萬元之間
2化學動態學新趨勢 中研院原分所劉國平教授 120 萬元
3第十屆東亞化學反應研討會 中研院原分所張煥正教授 20 萬元
42005 年第 1 屆台越理論計算化學研討會 交通大學林明璋教授 10 萬元
5第八屆亞洲結晶學國際研討會 清華大學理學院張石麟院長120 萬元
6 2006 年台灣生物無機研討會 中研院化學所洪政雄教授 56 萬元
- 6 -
最 新 消 息
第 192 次(95629)中心審議會決議
(一) 同意推薦下列十四位教授為中心訪問教授生活費補助以不超過七天為限並須
給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Jean-Pascal Sutter
95101-109 鄭建中教授
Nano-porous architectures Molecule-based magnets Nano-magnets
法國Toulous(土魯士)國家化學研究院資深
研究員
補助教授級生活
費及機票費
2 Junji Inanaga 951018-1024 方俊民教授
鑭系金屬有機化學不
對稱及官能性有機合成
日本九州大學教授 補助教授級生活
費及機票費
3 Donald H Levy 951210-1216 劉國平教授
Laser spectroscopy in supersonic molecular beams
Professor the University of Chicago USA
補助院士級生活
費及機票費
4 Henry Shaefer 951210-1216 劉國平教授
理論化學 Professor the University of Georgia USA
補助院士級生活
費及機票費
5 John C Tully 951210-1216 劉國平教授
理論發展分子動力學 Professor Yale University USA
補助院士級生活
費及機票費
6 Thomas T Tidwell 951024-1030 宋光生教授
Destabilized carbocations Ketene chemistry Aromaticity and Antiaromaticity
Professor Univ of Toronto Canada President of Canadian Chemical Society
1補助教授級生
活費及機票費
2請安排與中國
化學會會長見
面並在台北地
區增加一場演
講 7 John Ewart McGrady 9511 金必耀教授
量子化學計算化學 Professor of Computational Chemistry Univ of Glasgow UK
補助教授級生活
費及機票費
8 Hisao Nishiyama 95911-917 鄭建鴻教授
不對稱催化反應有機
合成 日本名古屋大學教授 補助教授級生活
費及機票費
9 Martin Head-Gordon 95129-1219 許昭萍博士
Theoretical Chemistry Electronic Structure Calculations
Professor Univ of California(Berkeley) USA
補助教授級生活
費及機票費
10 Masakatsu Shibasaki 951123-1129 王伯昌教授
生物有機有機合成
藥物化學 Professor The University of Tokyo Japan
補助教授級生活
費及機票費
- 7 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 11 Daniel G Nocera
951123-1129 王伯昌教授
奈米材料能源開發
電子轉移 Professor Massachusetts Institute of Technology USA
補助教授級生活
費及機票費
12Koichi Ohno 951121-26 游靜惠教授
Theoretical Chemistry Professor Tohoku University Japan
補助教授級生活
費及機票費
13Satoshi Yabushita 951121-26 游靜惠教授
Theoretical Chemistry Professor Keio University Japan
補助教授級生活
費及機票費
14 Laren M Tolbert 951119-26 陳建添教授
Organic photochemistryPhotobiology Electronic materials
Professor Associate Editor for the Journal of the American Chemical Society
補助教授級生活
費及機票費
(二) 同意推薦下列十位教授為國科會國際科技人士短期訪問教授生活費補助以不超
過七天為限並須給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Ann Mary Chippindale
95101-108 王素蘭教授
Solid State Chemistry Professor The University of Reading UK
補助教授級生活費及機票費
2 Steven Chu 951210-1216 倪其焜博士
物理應用物理 諾貝爾得主 Director Lawrence Berkeley National Laboratory USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 3 F Sherwood Rowland
951210-1216 倪其焜博士
Atmospheric Chemistry Chemical Kinetics
諾貝爾得主 Professor University of California Irvine USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶機票費
4 Dudley R Herschbach 951210-1216 倪其焜博士
Chemical Physics 諾貝爾得主 Professor Harvard University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 5J ohn B Fenn
951210-1216 倪其焜博士
Analytical chemistry 諾貝爾得主 Professor Virginia Commonwealth University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費
- 8 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 6 John C Polanyi
951210-1216 倪其焜博士
物理化學 諾貝爾得主 Professor Toronto University Canada
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 7 Chul-Ho Jun 951021-1027 鄭建鴻教授
催化反應金屬有機綠色化學
Professor Yonsei University Korea
補助教授級生活費及機票費
8 Nakeheol Jeong 951016-1021 陳竹亭教授
Organic Chemistry Professor Korea University Korea
補助教授級生活費及機票費
9 Hiroyuki Isobe 95111-116 陳竹亭教授
Organic Chemistry Associate Professor The University of Tokyo Japan
補助教授級生活費及機票費
10 Peter H Seeberger 95118-1113 洪上程教授
Organic Synthesis Carbohydrate Chemistry
Professor Eidgenossische Technische Hochschule Zurich Germany
補助教授級生活費及機票費
(三) 同意推薦下列研討會為國科會國際研討會
會 議 名 稱 建 議 補 助 經 費 備 註
1第八屆亞洲結晶學國際研討會 1200000 元
2 2006 年台灣生物無機研討會 560000 元
(四) 同意補助下列研討會經費如下
會 議 名 稱 補助金額 備 註
理論與計算化學研討會 49000 元 請檢據實報實銷
- 9 -
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
二中心訪問教授
姓名來訪日期及連絡人 主要專長 現職 1 Gary W Brudvig 94101-14 俞聖法博士
生物無機 Prof Yale University USA
2G M Hieftje 941015-22 林金全教授
原子分析光譜 儀器分析 感應器
Prof Indiana University USA
3Paul R Haddad 941016-23
林敬二教授
Liquid Chromatography Capillary Electrophoresis Ion Chromatography
Prof Univ of Tasmania Australian
4Eric Bakker 941014-20
林孟山教授
Potentiometry at Trace Levels Amperometric Ion Sensors
Prof Auburn University USA
5Alois FŰRSTNER 941028-31 劉行讓教授
Carbohydrate Chemistry Organic Synthesis Organometallic Chemistry
Prof the University of Dortmund Germany
6Michael J Krisch 941026-31
劉行讓教授
Organic Synthesis Organometallic Chemistry Catalysis
Prof University of Texas at Austin USA
7Frederick G West 941028-31 劉行讓教授
Synthetic Organic Chemistry Natural Products Chemistry Medicinal Chemistry
Prof University of Alberta Canada
8G Pattenden 941028-31 劉行讓教授
Synthetic Organic Natural Products ChemistryMedicinal Chemistry
Prof University of Nottingham United Kingdom
9A Ajayaghosh 94116-12 汪根欉教授
高分子超分子化學 印度國家科學工業研究委員會
研究員
10Charles P Casey 941118-26 江旭禎教授
生物有機化學 Prof Univ of Wisconsin-Madison USA
11 Andrew B Holmes 941123-26 陶雨台教授
Bioorganic Chemistry Polymeric Organic Materials Anticancer agents
Prof Melbourne University Australia
12 John P Fackler Jr 95320-326 劉鎮維教授
Inorganic Chemistry Professor Texas AampM Univ USA
- 2 -
姓名來訪日期及連絡人 主要專長 現職 13Robert P Lemieux
95115-121
陳建添教授
有機材料液晶光學開關 Professor Queenrsquos Univ Kingston Canada
14Wayne L Gladfelter 95226-34 吉凱明教授
Organometallic and Inorganic Synthesis Nanocrystalspf solid state materials Ceramic Material Chemistry
Professor amp Chair Univ of Minnesota USA
15Charles G Riordan 95319-325
廖文峰教授
Bioinorganic Chemistry Professor amp Chair Univ of Delaware USA
16 Kazuhiko Nakatani 9535-311
張一知教授
生化有機DNA 定位選擇性斷
序DNA 定位選擇性鍵結
Prof The Institute of Scientific and Industrial Res Osaka Univ Japan
17 Jean-Jacques Girerd 951-5 月(未定) 彭旭明教授
生物無機化學磁性化學 Prof amp Director Univ Paris-sud France
18 Jan-Erling Baumlckvall 95312-318 陸天堯教授
Organic Chemistry 結合有機金屬化學及酵素催
化反應的先驅者
Prof Stockholms Univ Sweden
19 Axel G Griesbeck 953 28-42
楊吉水教授
有機光化學 有機化學
ProfUniversity of Cologne Germany
20 Hellmut Eckert 95223-227 陳振中教授
Solid state nuclear magnetic resonance spectroscopy techniques
Prof University of Muenster Germany
21 Martin Quack 953 14-320
李遠鵬教授
Molecular Kinetics and Spectroscopy
ETH Zuumlrich Labortorium fuumlr Physikalische chemie ETH Switzerland
22 Andre Ayral 9558-514 趙桂蓉教授
膠體化學無機薄膜及材料 Prof University Montpellier II France
23Johannes G Vos 9562-610 季昀教授
無機化學有機金屬 Professor School of Chemical Sciences Dublin City Univ Germany
- 3 -
三國科會短期訪問教授審查
姓名來訪日期及連絡人 主 要 專 長 現 職 1Ziling(Ben) Xue 941028-31 劉瑞雄教授
Synthetic and Mechanistic Orgaometallic Inorganic Chemistry
Prof University of Tennessee USA
2SonBinh T Nguyen 941028-31 劉瑞雄教授
Catalysis Materials Chemistry PohotchemistryPhotocatalysis
Prof Northwestern University USA
3Omar M Yaghi 941028-31 劉瑞雄教授
Low density solids Hierarchical structures Smart crystalline sponges
Prof University of Michigan USA
4Kiyokatsu Jinno 941014-20 林敬二教授
High performance Liquid Chromatography Capillary Electrophoresis
Prof Toyohashi Univ of Technology Japan
5Shigeru Terabe 941016-23
林敬二教授
Capillary Electrophoresis Capillary Electrochromatography
Prof Univ of Hyogo Japan
6 Silvio Aime 94103-10 王雲銘教授
生物無機 Prof I F M University Italy
7 Teizo Kitagawa 94103-10 洪政雄教授
生物無機 Prof National Institutes of Natural Sciences Japan
8 Tetsuro Majima 941121-27 陳建添教授
Photochemistry Radiation Chemistry Nanoscience
Prof Osaka University Japan
9Jung-Il Jin 941123-27 陶雨台教授
光電材料 Prof Korea University Korea
10Chihaya Adachi 941123-27 陶雨台教授
光電材料 Prof Chitose Institute of Science and Technology Japan
11Robert Glaum 94913-916 王素蘭教授
無機固態化學 德國波昂大學教授
12Ramamoorthy A 94817-20 陳振中教授
NMR Associate Professor Univ of Michigan (Ann Arbor) USA
13 莊自強 941018-19 葉瑞銘教授
Polymer science Catalysis Functional materials
Prof The Penns Sate Univ USA
14 剛本正己
941018-19 葉瑞銘教授
Polymer Physics Polymer Eng Biomaterials
Associate Prof Toyota Technological Institute Japan
15 魏建謨 941120-23 葉華光教授
物理化學及放射化學 Prof Univ of Idaho USA
- 4 -
姓名來訪日期及連絡人 主 要 專 長 現 職
16Todd L Lowary 95430-56 劉行讓教授
Chemistry Glycobiology
Associate Prof The Univ of Alberta Canada
17Kwan Soo Kim 95212-218 洪上程教授
Organic synthesis Carbohydrate Chemistry
Professor Yonsei Univ Korea
18F Dean Toste 95423-429 陳建添教授
有機金屬催化 Assistant Prof Univ of California Berkeley USA
19 Mikio Takano 95320-325 劉如熹教授
Solid State Chemistry Prof Kyoto Univ Japan
20 Norio Miyaura 95430-56 陸天堯教授
有機合成化學 有機金屬化學
日本北海大學教授
21 Kazuko Matsumoto 941119-1124 劉陵崗教授
Chemistry 日本早稻田大學教授
22 Mitsuo Kira 95416-422 蘇明德教授
無機化學 合成化學
日本東北大學教授
23 Jacquelyn Gervay Hague 95310-315 林俊宏教授
Carbohydrate Chemistry Prof University of California Davis USA
24 David W C MacMillan 95310-316 劉陵崗教授
Organic Chemistry Prof The California Institute of Technology California USA
25Paul Jean Amoureux 941220-1227 丁尚武教授
Physics Electronics
Prof Lille-1 University France
26 Janet L Scott 95313-319 凌永健教授
有機合成 Prof Monash Univ Australia
27 Chris Strauss 953 13-319 凌永健教授
有機合成 Prof Monash Univ Australia
28 Milton Hearn 953 13-319 凌永健教授
分析化學 Prof Monash Univ Australia
29Takashi Ooi 95314-318 劉瑞雄教授
Organic Synthesis 日本京都大學副教授
- 5 -
姓名來訪日期及連絡人 主 要 專 長 現 職
30Nicholas Andrew Morrice 95312-321 陳淑慧教授
蛋白質體分析 Head of Proteomics NRC Research Support Scientist Univ of Dundee UK
31A J Arduengo III 95910-917 林志彪教授
Organic Chemistry Inorganic Chemistry
Professor Department of Chemistry The Univ of Alabama
32Kei Takeda 9564-610 王英基教授
Invention of new reactions Their mechanistic studies and synthetic applications
日本廣島大學教授
33裴堅(大陸科技人士) 95213-217 陸天堯教授
有機合成有機材料化學 北京大學化學學院教授
34Shiou-Jyh Hwu 9543-47 王素蘭教授
Solid State Chemistry Professor Clemson Univ USA
35陳守信教授 95516-525 林滄浪教授
X-ray and Neutron Scattering spectroscopy of Complex Fluids and Soft Matter
Professor Massachusetts Institute of Technology USA
36錢明仁教授 95514-67 陳貴賢教授
電化學 Professor University of North Texas USA
四國際研討會及兩岸研討會之審查
研 討 會 名 稱 申請人及單位 建議補助金額
1第十六屆國際磁共振學會研討會 中研院生醫所黃太煌教授 150萬至200萬元之間
2化學動態學新趨勢 中研院原分所劉國平教授 120 萬元
3第十屆東亞化學反應研討會 中研院原分所張煥正教授 20 萬元
42005 年第 1 屆台越理論計算化學研討會 交通大學林明璋教授 10 萬元
5第八屆亞洲結晶學國際研討會 清華大學理學院張石麟院長120 萬元
6 2006 年台灣生物無機研討會 中研院化學所洪政雄教授 56 萬元
- 6 -
最 新 消 息
第 192 次(95629)中心審議會決議
(一) 同意推薦下列十四位教授為中心訪問教授生活費補助以不超過七天為限並須
給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Jean-Pascal Sutter
95101-109 鄭建中教授
Nano-porous architectures Molecule-based magnets Nano-magnets
法國Toulous(土魯士)國家化學研究院資深
研究員
補助教授級生活
費及機票費
2 Junji Inanaga 951018-1024 方俊民教授
鑭系金屬有機化學不
對稱及官能性有機合成
日本九州大學教授 補助教授級生活
費及機票費
3 Donald H Levy 951210-1216 劉國平教授
Laser spectroscopy in supersonic molecular beams
Professor the University of Chicago USA
補助院士級生活
費及機票費
4 Henry Shaefer 951210-1216 劉國平教授
理論化學 Professor the University of Georgia USA
補助院士級生活
費及機票費
5 John C Tully 951210-1216 劉國平教授
理論發展分子動力學 Professor Yale University USA
補助院士級生活
費及機票費
6 Thomas T Tidwell 951024-1030 宋光生教授
Destabilized carbocations Ketene chemistry Aromaticity and Antiaromaticity
Professor Univ of Toronto Canada President of Canadian Chemical Society
1補助教授級生
活費及機票費
2請安排與中國
化學會會長見
面並在台北地
區增加一場演
講 7 John Ewart McGrady 9511 金必耀教授
量子化學計算化學 Professor of Computational Chemistry Univ of Glasgow UK
補助教授級生活
費及機票費
8 Hisao Nishiyama 95911-917 鄭建鴻教授
不對稱催化反應有機
合成 日本名古屋大學教授 補助教授級生活
費及機票費
9 Martin Head-Gordon 95129-1219 許昭萍博士
Theoretical Chemistry Electronic Structure Calculations
Professor Univ of California(Berkeley) USA
補助教授級生活
費及機票費
10 Masakatsu Shibasaki 951123-1129 王伯昌教授
生物有機有機合成
藥物化學 Professor The University of Tokyo Japan
補助教授級生活
費及機票費
- 7 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 11 Daniel G Nocera
951123-1129 王伯昌教授
奈米材料能源開發
電子轉移 Professor Massachusetts Institute of Technology USA
補助教授級生活
費及機票費
12Koichi Ohno 951121-26 游靜惠教授
Theoretical Chemistry Professor Tohoku University Japan
補助教授級生活
費及機票費
13Satoshi Yabushita 951121-26 游靜惠教授
Theoretical Chemistry Professor Keio University Japan
補助教授級生活
費及機票費
14 Laren M Tolbert 951119-26 陳建添教授
Organic photochemistryPhotobiology Electronic materials
Professor Associate Editor for the Journal of the American Chemical Society
補助教授級生活
費及機票費
(二) 同意推薦下列十位教授為國科會國際科技人士短期訪問教授生活費補助以不超
過七天為限並須給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Ann Mary Chippindale
95101-108 王素蘭教授
Solid State Chemistry Professor The University of Reading UK
補助教授級生活費及機票費
2 Steven Chu 951210-1216 倪其焜博士
物理應用物理 諾貝爾得主 Director Lawrence Berkeley National Laboratory USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 3 F Sherwood Rowland
951210-1216 倪其焜博士
Atmospheric Chemistry Chemical Kinetics
諾貝爾得主 Professor University of California Irvine USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶機票費
4 Dudley R Herschbach 951210-1216 倪其焜博士
Chemical Physics 諾貝爾得主 Professor Harvard University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 5J ohn B Fenn
951210-1216 倪其焜博士
Analytical chemistry 諾貝爾得主 Professor Virginia Commonwealth University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費
- 8 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 6 John C Polanyi
951210-1216 倪其焜博士
物理化學 諾貝爾得主 Professor Toronto University Canada
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 7 Chul-Ho Jun 951021-1027 鄭建鴻教授
催化反應金屬有機綠色化學
Professor Yonsei University Korea
補助教授級生活費及機票費
8 Nakeheol Jeong 951016-1021 陳竹亭教授
Organic Chemistry Professor Korea University Korea
補助教授級生活費及機票費
9 Hiroyuki Isobe 95111-116 陳竹亭教授
Organic Chemistry Associate Professor The University of Tokyo Japan
補助教授級生活費及機票費
10 Peter H Seeberger 95118-1113 洪上程教授
Organic Synthesis Carbohydrate Chemistry
Professor Eidgenossische Technische Hochschule Zurich Germany
補助教授級生活費及機票費
(三) 同意推薦下列研討會為國科會國際研討會
會 議 名 稱 建 議 補 助 經 費 備 註
1第八屆亞洲結晶學國際研討會 1200000 元
2 2006 年台灣生物無機研討會 560000 元
(四) 同意補助下列研討會經費如下
會 議 名 稱 補助金額 備 註
理論與計算化學研討會 49000 元 請檢據實報實銷
- 9 -
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
姓名來訪日期及連絡人 主要專長 現職 13Robert P Lemieux
95115-121
陳建添教授
有機材料液晶光學開關 Professor Queenrsquos Univ Kingston Canada
14Wayne L Gladfelter 95226-34 吉凱明教授
Organometallic and Inorganic Synthesis Nanocrystalspf solid state materials Ceramic Material Chemistry
Professor amp Chair Univ of Minnesota USA
15Charles G Riordan 95319-325
廖文峰教授
Bioinorganic Chemistry Professor amp Chair Univ of Delaware USA
16 Kazuhiko Nakatani 9535-311
張一知教授
生化有機DNA 定位選擇性斷
序DNA 定位選擇性鍵結
Prof The Institute of Scientific and Industrial Res Osaka Univ Japan
17 Jean-Jacques Girerd 951-5 月(未定) 彭旭明教授
生物無機化學磁性化學 Prof amp Director Univ Paris-sud France
18 Jan-Erling Baumlckvall 95312-318 陸天堯教授
Organic Chemistry 結合有機金屬化學及酵素催
化反應的先驅者
Prof Stockholms Univ Sweden
19 Axel G Griesbeck 953 28-42
楊吉水教授
有機光化學 有機化學
ProfUniversity of Cologne Germany
20 Hellmut Eckert 95223-227 陳振中教授
Solid state nuclear magnetic resonance spectroscopy techniques
Prof University of Muenster Germany
21 Martin Quack 953 14-320
李遠鵬教授
Molecular Kinetics and Spectroscopy
ETH Zuumlrich Labortorium fuumlr Physikalische chemie ETH Switzerland
22 Andre Ayral 9558-514 趙桂蓉教授
膠體化學無機薄膜及材料 Prof University Montpellier II France
23Johannes G Vos 9562-610 季昀教授
無機化學有機金屬 Professor School of Chemical Sciences Dublin City Univ Germany
- 3 -
三國科會短期訪問教授審查
姓名來訪日期及連絡人 主 要 專 長 現 職 1Ziling(Ben) Xue 941028-31 劉瑞雄教授
Synthetic and Mechanistic Orgaometallic Inorganic Chemistry
Prof University of Tennessee USA
2SonBinh T Nguyen 941028-31 劉瑞雄教授
Catalysis Materials Chemistry PohotchemistryPhotocatalysis
Prof Northwestern University USA
3Omar M Yaghi 941028-31 劉瑞雄教授
Low density solids Hierarchical structures Smart crystalline sponges
Prof University of Michigan USA
4Kiyokatsu Jinno 941014-20 林敬二教授
High performance Liquid Chromatography Capillary Electrophoresis
Prof Toyohashi Univ of Technology Japan
5Shigeru Terabe 941016-23
林敬二教授
Capillary Electrophoresis Capillary Electrochromatography
Prof Univ of Hyogo Japan
6 Silvio Aime 94103-10 王雲銘教授
生物無機 Prof I F M University Italy
7 Teizo Kitagawa 94103-10 洪政雄教授
生物無機 Prof National Institutes of Natural Sciences Japan
8 Tetsuro Majima 941121-27 陳建添教授
Photochemistry Radiation Chemistry Nanoscience
Prof Osaka University Japan
9Jung-Il Jin 941123-27 陶雨台教授
光電材料 Prof Korea University Korea
10Chihaya Adachi 941123-27 陶雨台教授
光電材料 Prof Chitose Institute of Science and Technology Japan
11Robert Glaum 94913-916 王素蘭教授
無機固態化學 德國波昂大學教授
12Ramamoorthy A 94817-20 陳振中教授
NMR Associate Professor Univ of Michigan (Ann Arbor) USA
13 莊自強 941018-19 葉瑞銘教授
Polymer science Catalysis Functional materials
Prof The Penns Sate Univ USA
14 剛本正己
941018-19 葉瑞銘教授
Polymer Physics Polymer Eng Biomaterials
Associate Prof Toyota Technological Institute Japan
15 魏建謨 941120-23 葉華光教授
物理化學及放射化學 Prof Univ of Idaho USA
- 4 -
姓名來訪日期及連絡人 主 要 專 長 現 職
16Todd L Lowary 95430-56 劉行讓教授
Chemistry Glycobiology
Associate Prof The Univ of Alberta Canada
17Kwan Soo Kim 95212-218 洪上程教授
Organic synthesis Carbohydrate Chemistry
Professor Yonsei Univ Korea
18F Dean Toste 95423-429 陳建添教授
有機金屬催化 Assistant Prof Univ of California Berkeley USA
19 Mikio Takano 95320-325 劉如熹教授
Solid State Chemistry Prof Kyoto Univ Japan
20 Norio Miyaura 95430-56 陸天堯教授
有機合成化學 有機金屬化學
日本北海大學教授
21 Kazuko Matsumoto 941119-1124 劉陵崗教授
Chemistry 日本早稻田大學教授
22 Mitsuo Kira 95416-422 蘇明德教授
無機化學 合成化學
日本東北大學教授
23 Jacquelyn Gervay Hague 95310-315 林俊宏教授
Carbohydrate Chemistry Prof University of California Davis USA
24 David W C MacMillan 95310-316 劉陵崗教授
Organic Chemistry Prof The California Institute of Technology California USA
25Paul Jean Amoureux 941220-1227 丁尚武教授
Physics Electronics
Prof Lille-1 University France
26 Janet L Scott 95313-319 凌永健教授
有機合成 Prof Monash Univ Australia
27 Chris Strauss 953 13-319 凌永健教授
有機合成 Prof Monash Univ Australia
28 Milton Hearn 953 13-319 凌永健教授
分析化學 Prof Monash Univ Australia
29Takashi Ooi 95314-318 劉瑞雄教授
Organic Synthesis 日本京都大學副教授
- 5 -
姓名來訪日期及連絡人 主 要 專 長 現 職
30Nicholas Andrew Morrice 95312-321 陳淑慧教授
蛋白質體分析 Head of Proteomics NRC Research Support Scientist Univ of Dundee UK
31A J Arduengo III 95910-917 林志彪教授
Organic Chemistry Inorganic Chemistry
Professor Department of Chemistry The Univ of Alabama
32Kei Takeda 9564-610 王英基教授
Invention of new reactions Their mechanistic studies and synthetic applications
日本廣島大學教授
33裴堅(大陸科技人士) 95213-217 陸天堯教授
有機合成有機材料化學 北京大學化學學院教授
34Shiou-Jyh Hwu 9543-47 王素蘭教授
Solid State Chemistry Professor Clemson Univ USA
35陳守信教授 95516-525 林滄浪教授
X-ray and Neutron Scattering spectroscopy of Complex Fluids and Soft Matter
Professor Massachusetts Institute of Technology USA
36錢明仁教授 95514-67 陳貴賢教授
電化學 Professor University of North Texas USA
四國際研討會及兩岸研討會之審查
研 討 會 名 稱 申請人及單位 建議補助金額
1第十六屆國際磁共振學會研討會 中研院生醫所黃太煌教授 150萬至200萬元之間
2化學動態學新趨勢 中研院原分所劉國平教授 120 萬元
3第十屆東亞化學反應研討會 中研院原分所張煥正教授 20 萬元
42005 年第 1 屆台越理論計算化學研討會 交通大學林明璋教授 10 萬元
5第八屆亞洲結晶學國際研討會 清華大學理學院張石麟院長120 萬元
6 2006 年台灣生物無機研討會 中研院化學所洪政雄教授 56 萬元
- 6 -
最 新 消 息
第 192 次(95629)中心審議會決議
(一) 同意推薦下列十四位教授為中心訪問教授生活費補助以不超過七天為限並須
給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Jean-Pascal Sutter
95101-109 鄭建中教授
Nano-porous architectures Molecule-based magnets Nano-magnets
法國Toulous(土魯士)國家化學研究院資深
研究員
補助教授級生活
費及機票費
2 Junji Inanaga 951018-1024 方俊民教授
鑭系金屬有機化學不
對稱及官能性有機合成
日本九州大學教授 補助教授級生活
費及機票費
3 Donald H Levy 951210-1216 劉國平教授
Laser spectroscopy in supersonic molecular beams
Professor the University of Chicago USA
補助院士級生活
費及機票費
4 Henry Shaefer 951210-1216 劉國平教授
理論化學 Professor the University of Georgia USA
補助院士級生活
費及機票費
5 John C Tully 951210-1216 劉國平教授
理論發展分子動力學 Professor Yale University USA
補助院士級生活
費及機票費
6 Thomas T Tidwell 951024-1030 宋光生教授
Destabilized carbocations Ketene chemistry Aromaticity and Antiaromaticity
Professor Univ of Toronto Canada President of Canadian Chemical Society
1補助教授級生
活費及機票費
2請安排與中國
化學會會長見
面並在台北地
區增加一場演
講 7 John Ewart McGrady 9511 金必耀教授
量子化學計算化學 Professor of Computational Chemistry Univ of Glasgow UK
補助教授級生活
費及機票費
8 Hisao Nishiyama 95911-917 鄭建鴻教授
不對稱催化反應有機
合成 日本名古屋大學教授 補助教授級生活
費及機票費
9 Martin Head-Gordon 95129-1219 許昭萍博士
Theoretical Chemistry Electronic Structure Calculations
Professor Univ of California(Berkeley) USA
補助教授級生活
費及機票費
10 Masakatsu Shibasaki 951123-1129 王伯昌教授
生物有機有機合成
藥物化學 Professor The University of Tokyo Japan
補助教授級生活
費及機票費
- 7 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 11 Daniel G Nocera
951123-1129 王伯昌教授
奈米材料能源開發
電子轉移 Professor Massachusetts Institute of Technology USA
補助教授級生活
費及機票費
12Koichi Ohno 951121-26 游靜惠教授
Theoretical Chemistry Professor Tohoku University Japan
補助教授級生活
費及機票費
13Satoshi Yabushita 951121-26 游靜惠教授
Theoretical Chemistry Professor Keio University Japan
補助教授級生活
費及機票費
14 Laren M Tolbert 951119-26 陳建添教授
Organic photochemistryPhotobiology Electronic materials
Professor Associate Editor for the Journal of the American Chemical Society
補助教授級生活
費及機票費
(二) 同意推薦下列十位教授為國科會國際科技人士短期訪問教授生活費補助以不超
過七天為限並須給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Ann Mary Chippindale
95101-108 王素蘭教授
Solid State Chemistry Professor The University of Reading UK
補助教授級生活費及機票費
2 Steven Chu 951210-1216 倪其焜博士
物理應用物理 諾貝爾得主 Director Lawrence Berkeley National Laboratory USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 3 F Sherwood Rowland
951210-1216 倪其焜博士
Atmospheric Chemistry Chemical Kinetics
諾貝爾得主 Professor University of California Irvine USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶機票費
4 Dudley R Herschbach 951210-1216 倪其焜博士
Chemical Physics 諾貝爾得主 Professor Harvard University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 5J ohn B Fenn
951210-1216 倪其焜博士
Analytical chemistry 諾貝爾得主 Professor Virginia Commonwealth University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費
- 8 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 6 John C Polanyi
951210-1216 倪其焜博士
物理化學 諾貝爾得主 Professor Toronto University Canada
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 7 Chul-Ho Jun 951021-1027 鄭建鴻教授
催化反應金屬有機綠色化學
Professor Yonsei University Korea
補助教授級生活費及機票費
8 Nakeheol Jeong 951016-1021 陳竹亭教授
Organic Chemistry Professor Korea University Korea
補助教授級生活費及機票費
9 Hiroyuki Isobe 95111-116 陳竹亭教授
Organic Chemistry Associate Professor The University of Tokyo Japan
補助教授級生活費及機票費
10 Peter H Seeberger 95118-1113 洪上程教授
Organic Synthesis Carbohydrate Chemistry
Professor Eidgenossische Technische Hochschule Zurich Germany
補助教授級生活費及機票費
(三) 同意推薦下列研討會為國科會國際研討會
會 議 名 稱 建 議 補 助 經 費 備 註
1第八屆亞洲結晶學國際研討會 1200000 元
2 2006 年台灣生物無機研討會 560000 元
(四) 同意補助下列研討會經費如下
會 議 名 稱 補助金額 備 註
理論與計算化學研討會 49000 元 請檢據實報實銷
- 9 -
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
三國科會短期訪問教授審查
姓名來訪日期及連絡人 主 要 專 長 現 職 1Ziling(Ben) Xue 941028-31 劉瑞雄教授
Synthetic and Mechanistic Orgaometallic Inorganic Chemistry
Prof University of Tennessee USA
2SonBinh T Nguyen 941028-31 劉瑞雄教授
Catalysis Materials Chemistry PohotchemistryPhotocatalysis
Prof Northwestern University USA
3Omar M Yaghi 941028-31 劉瑞雄教授
Low density solids Hierarchical structures Smart crystalline sponges
Prof University of Michigan USA
4Kiyokatsu Jinno 941014-20 林敬二教授
High performance Liquid Chromatography Capillary Electrophoresis
Prof Toyohashi Univ of Technology Japan
5Shigeru Terabe 941016-23
林敬二教授
Capillary Electrophoresis Capillary Electrochromatography
Prof Univ of Hyogo Japan
6 Silvio Aime 94103-10 王雲銘教授
生物無機 Prof I F M University Italy
7 Teizo Kitagawa 94103-10 洪政雄教授
生物無機 Prof National Institutes of Natural Sciences Japan
8 Tetsuro Majima 941121-27 陳建添教授
Photochemistry Radiation Chemistry Nanoscience
Prof Osaka University Japan
9Jung-Il Jin 941123-27 陶雨台教授
光電材料 Prof Korea University Korea
10Chihaya Adachi 941123-27 陶雨台教授
光電材料 Prof Chitose Institute of Science and Technology Japan
11Robert Glaum 94913-916 王素蘭教授
無機固態化學 德國波昂大學教授
12Ramamoorthy A 94817-20 陳振中教授
NMR Associate Professor Univ of Michigan (Ann Arbor) USA
13 莊自強 941018-19 葉瑞銘教授
Polymer science Catalysis Functional materials
Prof The Penns Sate Univ USA
14 剛本正己
941018-19 葉瑞銘教授
Polymer Physics Polymer Eng Biomaterials
Associate Prof Toyota Technological Institute Japan
15 魏建謨 941120-23 葉華光教授
物理化學及放射化學 Prof Univ of Idaho USA
- 4 -
姓名來訪日期及連絡人 主 要 專 長 現 職
16Todd L Lowary 95430-56 劉行讓教授
Chemistry Glycobiology
Associate Prof The Univ of Alberta Canada
17Kwan Soo Kim 95212-218 洪上程教授
Organic synthesis Carbohydrate Chemistry
Professor Yonsei Univ Korea
18F Dean Toste 95423-429 陳建添教授
有機金屬催化 Assistant Prof Univ of California Berkeley USA
19 Mikio Takano 95320-325 劉如熹教授
Solid State Chemistry Prof Kyoto Univ Japan
20 Norio Miyaura 95430-56 陸天堯教授
有機合成化學 有機金屬化學
日本北海大學教授
21 Kazuko Matsumoto 941119-1124 劉陵崗教授
Chemistry 日本早稻田大學教授
22 Mitsuo Kira 95416-422 蘇明德教授
無機化學 合成化學
日本東北大學教授
23 Jacquelyn Gervay Hague 95310-315 林俊宏教授
Carbohydrate Chemistry Prof University of California Davis USA
24 David W C MacMillan 95310-316 劉陵崗教授
Organic Chemistry Prof The California Institute of Technology California USA
25Paul Jean Amoureux 941220-1227 丁尚武教授
Physics Electronics
Prof Lille-1 University France
26 Janet L Scott 95313-319 凌永健教授
有機合成 Prof Monash Univ Australia
27 Chris Strauss 953 13-319 凌永健教授
有機合成 Prof Monash Univ Australia
28 Milton Hearn 953 13-319 凌永健教授
分析化學 Prof Monash Univ Australia
29Takashi Ooi 95314-318 劉瑞雄教授
Organic Synthesis 日本京都大學副教授
- 5 -
姓名來訪日期及連絡人 主 要 專 長 現 職
30Nicholas Andrew Morrice 95312-321 陳淑慧教授
蛋白質體分析 Head of Proteomics NRC Research Support Scientist Univ of Dundee UK
31A J Arduengo III 95910-917 林志彪教授
Organic Chemistry Inorganic Chemistry
Professor Department of Chemistry The Univ of Alabama
32Kei Takeda 9564-610 王英基教授
Invention of new reactions Their mechanistic studies and synthetic applications
日本廣島大學教授
33裴堅(大陸科技人士) 95213-217 陸天堯教授
有機合成有機材料化學 北京大學化學學院教授
34Shiou-Jyh Hwu 9543-47 王素蘭教授
Solid State Chemistry Professor Clemson Univ USA
35陳守信教授 95516-525 林滄浪教授
X-ray and Neutron Scattering spectroscopy of Complex Fluids and Soft Matter
Professor Massachusetts Institute of Technology USA
36錢明仁教授 95514-67 陳貴賢教授
電化學 Professor University of North Texas USA
四國際研討會及兩岸研討會之審查
研 討 會 名 稱 申請人及單位 建議補助金額
1第十六屆國際磁共振學會研討會 中研院生醫所黃太煌教授 150萬至200萬元之間
2化學動態學新趨勢 中研院原分所劉國平教授 120 萬元
3第十屆東亞化學反應研討會 中研院原分所張煥正教授 20 萬元
42005 年第 1 屆台越理論計算化學研討會 交通大學林明璋教授 10 萬元
5第八屆亞洲結晶學國際研討會 清華大學理學院張石麟院長120 萬元
6 2006 年台灣生物無機研討會 中研院化學所洪政雄教授 56 萬元
- 6 -
最 新 消 息
第 192 次(95629)中心審議會決議
(一) 同意推薦下列十四位教授為中心訪問教授生活費補助以不超過七天為限並須
給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Jean-Pascal Sutter
95101-109 鄭建中教授
Nano-porous architectures Molecule-based magnets Nano-magnets
法國Toulous(土魯士)國家化學研究院資深
研究員
補助教授級生活
費及機票費
2 Junji Inanaga 951018-1024 方俊民教授
鑭系金屬有機化學不
對稱及官能性有機合成
日本九州大學教授 補助教授級生活
費及機票費
3 Donald H Levy 951210-1216 劉國平教授
Laser spectroscopy in supersonic molecular beams
Professor the University of Chicago USA
補助院士級生活
費及機票費
4 Henry Shaefer 951210-1216 劉國平教授
理論化學 Professor the University of Georgia USA
補助院士級生活
費及機票費
5 John C Tully 951210-1216 劉國平教授
理論發展分子動力學 Professor Yale University USA
補助院士級生活
費及機票費
6 Thomas T Tidwell 951024-1030 宋光生教授
Destabilized carbocations Ketene chemistry Aromaticity and Antiaromaticity
Professor Univ of Toronto Canada President of Canadian Chemical Society
1補助教授級生
活費及機票費
2請安排與中國
化學會會長見
面並在台北地
區增加一場演
講 7 John Ewart McGrady 9511 金必耀教授
量子化學計算化學 Professor of Computational Chemistry Univ of Glasgow UK
補助教授級生活
費及機票費
8 Hisao Nishiyama 95911-917 鄭建鴻教授
不對稱催化反應有機
合成 日本名古屋大學教授 補助教授級生活
費及機票費
9 Martin Head-Gordon 95129-1219 許昭萍博士
Theoretical Chemistry Electronic Structure Calculations
Professor Univ of California(Berkeley) USA
補助教授級生活
費及機票費
10 Masakatsu Shibasaki 951123-1129 王伯昌教授
生物有機有機合成
藥物化學 Professor The University of Tokyo Japan
補助教授級生活
費及機票費
- 7 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 11 Daniel G Nocera
951123-1129 王伯昌教授
奈米材料能源開發
電子轉移 Professor Massachusetts Institute of Technology USA
補助教授級生活
費及機票費
12Koichi Ohno 951121-26 游靜惠教授
Theoretical Chemistry Professor Tohoku University Japan
補助教授級生活
費及機票費
13Satoshi Yabushita 951121-26 游靜惠教授
Theoretical Chemistry Professor Keio University Japan
補助教授級生活
費及機票費
14 Laren M Tolbert 951119-26 陳建添教授
Organic photochemistryPhotobiology Electronic materials
Professor Associate Editor for the Journal of the American Chemical Society
補助教授級生活
費及機票費
(二) 同意推薦下列十位教授為國科會國際科技人士短期訪問教授生活費補助以不超
過七天為限並須給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Ann Mary Chippindale
95101-108 王素蘭教授
Solid State Chemistry Professor The University of Reading UK
補助教授級生活費及機票費
2 Steven Chu 951210-1216 倪其焜博士
物理應用物理 諾貝爾得主 Director Lawrence Berkeley National Laboratory USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 3 F Sherwood Rowland
951210-1216 倪其焜博士
Atmospheric Chemistry Chemical Kinetics
諾貝爾得主 Professor University of California Irvine USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶機票費
4 Dudley R Herschbach 951210-1216 倪其焜博士
Chemical Physics 諾貝爾得主 Professor Harvard University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 5J ohn B Fenn
951210-1216 倪其焜博士
Analytical chemistry 諾貝爾得主 Professor Virginia Commonwealth University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費
- 8 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 6 John C Polanyi
951210-1216 倪其焜博士
物理化學 諾貝爾得主 Professor Toronto University Canada
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 7 Chul-Ho Jun 951021-1027 鄭建鴻教授
催化反應金屬有機綠色化學
Professor Yonsei University Korea
補助教授級生活費及機票費
8 Nakeheol Jeong 951016-1021 陳竹亭教授
Organic Chemistry Professor Korea University Korea
補助教授級生活費及機票費
9 Hiroyuki Isobe 95111-116 陳竹亭教授
Organic Chemistry Associate Professor The University of Tokyo Japan
補助教授級生活費及機票費
10 Peter H Seeberger 95118-1113 洪上程教授
Organic Synthesis Carbohydrate Chemistry
Professor Eidgenossische Technische Hochschule Zurich Germany
補助教授級生活費及機票費
(三) 同意推薦下列研討會為國科會國際研討會
會 議 名 稱 建 議 補 助 經 費 備 註
1第八屆亞洲結晶學國際研討會 1200000 元
2 2006 年台灣生物無機研討會 560000 元
(四) 同意補助下列研討會經費如下
會 議 名 稱 補助金額 備 註
理論與計算化學研討會 49000 元 請檢據實報實銷
- 9 -
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
姓名來訪日期及連絡人 主 要 專 長 現 職
16Todd L Lowary 95430-56 劉行讓教授
Chemistry Glycobiology
Associate Prof The Univ of Alberta Canada
17Kwan Soo Kim 95212-218 洪上程教授
Organic synthesis Carbohydrate Chemistry
Professor Yonsei Univ Korea
18F Dean Toste 95423-429 陳建添教授
有機金屬催化 Assistant Prof Univ of California Berkeley USA
19 Mikio Takano 95320-325 劉如熹教授
Solid State Chemistry Prof Kyoto Univ Japan
20 Norio Miyaura 95430-56 陸天堯教授
有機合成化學 有機金屬化學
日本北海大學教授
21 Kazuko Matsumoto 941119-1124 劉陵崗教授
Chemistry 日本早稻田大學教授
22 Mitsuo Kira 95416-422 蘇明德教授
無機化學 合成化學
日本東北大學教授
23 Jacquelyn Gervay Hague 95310-315 林俊宏教授
Carbohydrate Chemistry Prof University of California Davis USA
24 David W C MacMillan 95310-316 劉陵崗教授
Organic Chemistry Prof The California Institute of Technology California USA
25Paul Jean Amoureux 941220-1227 丁尚武教授
Physics Electronics
Prof Lille-1 University France
26 Janet L Scott 95313-319 凌永健教授
有機合成 Prof Monash Univ Australia
27 Chris Strauss 953 13-319 凌永健教授
有機合成 Prof Monash Univ Australia
28 Milton Hearn 953 13-319 凌永健教授
分析化學 Prof Monash Univ Australia
29Takashi Ooi 95314-318 劉瑞雄教授
Organic Synthesis 日本京都大學副教授
- 5 -
姓名來訪日期及連絡人 主 要 專 長 現 職
30Nicholas Andrew Morrice 95312-321 陳淑慧教授
蛋白質體分析 Head of Proteomics NRC Research Support Scientist Univ of Dundee UK
31A J Arduengo III 95910-917 林志彪教授
Organic Chemistry Inorganic Chemistry
Professor Department of Chemistry The Univ of Alabama
32Kei Takeda 9564-610 王英基教授
Invention of new reactions Their mechanistic studies and synthetic applications
日本廣島大學教授
33裴堅(大陸科技人士) 95213-217 陸天堯教授
有機合成有機材料化學 北京大學化學學院教授
34Shiou-Jyh Hwu 9543-47 王素蘭教授
Solid State Chemistry Professor Clemson Univ USA
35陳守信教授 95516-525 林滄浪教授
X-ray and Neutron Scattering spectroscopy of Complex Fluids and Soft Matter
Professor Massachusetts Institute of Technology USA
36錢明仁教授 95514-67 陳貴賢教授
電化學 Professor University of North Texas USA
四國際研討會及兩岸研討會之審查
研 討 會 名 稱 申請人及單位 建議補助金額
1第十六屆國際磁共振學會研討會 中研院生醫所黃太煌教授 150萬至200萬元之間
2化學動態學新趨勢 中研院原分所劉國平教授 120 萬元
3第十屆東亞化學反應研討會 中研院原分所張煥正教授 20 萬元
42005 年第 1 屆台越理論計算化學研討會 交通大學林明璋教授 10 萬元
5第八屆亞洲結晶學國際研討會 清華大學理學院張石麟院長120 萬元
6 2006 年台灣生物無機研討會 中研院化學所洪政雄教授 56 萬元
- 6 -
最 新 消 息
第 192 次(95629)中心審議會決議
(一) 同意推薦下列十四位教授為中心訪問教授生活費補助以不超過七天為限並須
給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Jean-Pascal Sutter
95101-109 鄭建中教授
Nano-porous architectures Molecule-based magnets Nano-magnets
法國Toulous(土魯士)國家化學研究院資深
研究員
補助教授級生活
費及機票費
2 Junji Inanaga 951018-1024 方俊民教授
鑭系金屬有機化學不
對稱及官能性有機合成
日本九州大學教授 補助教授級生活
費及機票費
3 Donald H Levy 951210-1216 劉國平教授
Laser spectroscopy in supersonic molecular beams
Professor the University of Chicago USA
補助院士級生活
費及機票費
4 Henry Shaefer 951210-1216 劉國平教授
理論化學 Professor the University of Georgia USA
補助院士級生活
費及機票費
5 John C Tully 951210-1216 劉國平教授
理論發展分子動力學 Professor Yale University USA
補助院士級生活
費及機票費
6 Thomas T Tidwell 951024-1030 宋光生教授
Destabilized carbocations Ketene chemistry Aromaticity and Antiaromaticity
Professor Univ of Toronto Canada President of Canadian Chemical Society
1補助教授級生
活費及機票費
2請安排與中國
化學會會長見
面並在台北地
區增加一場演
講 7 John Ewart McGrady 9511 金必耀教授
量子化學計算化學 Professor of Computational Chemistry Univ of Glasgow UK
補助教授級生活
費及機票費
8 Hisao Nishiyama 95911-917 鄭建鴻教授
不對稱催化反應有機
合成 日本名古屋大學教授 補助教授級生活
費及機票費
9 Martin Head-Gordon 95129-1219 許昭萍博士
Theoretical Chemistry Electronic Structure Calculations
Professor Univ of California(Berkeley) USA
補助教授級生活
費及機票費
10 Masakatsu Shibasaki 951123-1129 王伯昌教授
生物有機有機合成
藥物化學 Professor The University of Tokyo Japan
補助教授級生活
費及機票費
- 7 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 11 Daniel G Nocera
951123-1129 王伯昌教授
奈米材料能源開發
電子轉移 Professor Massachusetts Institute of Technology USA
補助教授級生活
費及機票費
12Koichi Ohno 951121-26 游靜惠教授
Theoretical Chemistry Professor Tohoku University Japan
補助教授級生活
費及機票費
13Satoshi Yabushita 951121-26 游靜惠教授
Theoretical Chemistry Professor Keio University Japan
補助教授級生活
費及機票費
14 Laren M Tolbert 951119-26 陳建添教授
Organic photochemistryPhotobiology Electronic materials
Professor Associate Editor for the Journal of the American Chemical Society
補助教授級生活
費及機票費
(二) 同意推薦下列十位教授為國科會國際科技人士短期訪問教授生活費補助以不超
過七天為限並須給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Ann Mary Chippindale
95101-108 王素蘭教授
Solid State Chemistry Professor The University of Reading UK
補助教授級生活費及機票費
2 Steven Chu 951210-1216 倪其焜博士
物理應用物理 諾貝爾得主 Director Lawrence Berkeley National Laboratory USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 3 F Sherwood Rowland
951210-1216 倪其焜博士
Atmospheric Chemistry Chemical Kinetics
諾貝爾得主 Professor University of California Irvine USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶機票費
4 Dudley R Herschbach 951210-1216 倪其焜博士
Chemical Physics 諾貝爾得主 Professor Harvard University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 5J ohn B Fenn
951210-1216 倪其焜博士
Analytical chemistry 諾貝爾得主 Professor Virginia Commonwealth University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費
- 8 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 6 John C Polanyi
951210-1216 倪其焜博士
物理化學 諾貝爾得主 Professor Toronto University Canada
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 7 Chul-Ho Jun 951021-1027 鄭建鴻教授
催化反應金屬有機綠色化學
Professor Yonsei University Korea
補助教授級生活費及機票費
8 Nakeheol Jeong 951016-1021 陳竹亭教授
Organic Chemistry Professor Korea University Korea
補助教授級生活費及機票費
9 Hiroyuki Isobe 95111-116 陳竹亭教授
Organic Chemistry Associate Professor The University of Tokyo Japan
補助教授級生活費及機票費
10 Peter H Seeberger 95118-1113 洪上程教授
Organic Synthesis Carbohydrate Chemistry
Professor Eidgenossische Technische Hochschule Zurich Germany
補助教授級生活費及機票費
(三) 同意推薦下列研討會為國科會國際研討會
會 議 名 稱 建 議 補 助 經 費 備 註
1第八屆亞洲結晶學國際研討會 1200000 元
2 2006 年台灣生物無機研討會 560000 元
(四) 同意補助下列研討會經費如下
會 議 名 稱 補助金額 備 註
理論與計算化學研討會 49000 元 請檢據實報實銷
- 9 -
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
姓名來訪日期及連絡人 主 要 專 長 現 職
30Nicholas Andrew Morrice 95312-321 陳淑慧教授
蛋白質體分析 Head of Proteomics NRC Research Support Scientist Univ of Dundee UK
31A J Arduengo III 95910-917 林志彪教授
Organic Chemistry Inorganic Chemistry
Professor Department of Chemistry The Univ of Alabama
32Kei Takeda 9564-610 王英基教授
Invention of new reactions Their mechanistic studies and synthetic applications
日本廣島大學教授
33裴堅(大陸科技人士) 95213-217 陸天堯教授
有機合成有機材料化學 北京大學化學學院教授
34Shiou-Jyh Hwu 9543-47 王素蘭教授
Solid State Chemistry Professor Clemson Univ USA
35陳守信教授 95516-525 林滄浪教授
X-ray and Neutron Scattering spectroscopy of Complex Fluids and Soft Matter
Professor Massachusetts Institute of Technology USA
36錢明仁教授 95514-67 陳貴賢教授
電化學 Professor University of North Texas USA
四國際研討會及兩岸研討會之審查
研 討 會 名 稱 申請人及單位 建議補助金額
1第十六屆國際磁共振學會研討會 中研院生醫所黃太煌教授 150萬至200萬元之間
2化學動態學新趨勢 中研院原分所劉國平教授 120 萬元
3第十屆東亞化學反應研討會 中研院原分所張煥正教授 20 萬元
42005 年第 1 屆台越理論計算化學研討會 交通大學林明璋教授 10 萬元
5第八屆亞洲結晶學國際研討會 清華大學理學院張石麟院長120 萬元
6 2006 年台灣生物無機研討會 中研院化學所洪政雄教授 56 萬元
- 6 -
最 新 消 息
第 192 次(95629)中心審議會決議
(一) 同意推薦下列十四位教授為中心訪問教授生活費補助以不超過七天為限並須
給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Jean-Pascal Sutter
95101-109 鄭建中教授
Nano-porous architectures Molecule-based magnets Nano-magnets
法國Toulous(土魯士)國家化學研究院資深
研究員
補助教授級生活
費及機票費
2 Junji Inanaga 951018-1024 方俊民教授
鑭系金屬有機化學不
對稱及官能性有機合成
日本九州大學教授 補助教授級生活
費及機票費
3 Donald H Levy 951210-1216 劉國平教授
Laser spectroscopy in supersonic molecular beams
Professor the University of Chicago USA
補助院士級生活
費及機票費
4 Henry Shaefer 951210-1216 劉國平教授
理論化學 Professor the University of Georgia USA
補助院士級生活
費及機票費
5 John C Tully 951210-1216 劉國平教授
理論發展分子動力學 Professor Yale University USA
補助院士級生活
費及機票費
6 Thomas T Tidwell 951024-1030 宋光生教授
Destabilized carbocations Ketene chemistry Aromaticity and Antiaromaticity
Professor Univ of Toronto Canada President of Canadian Chemical Society
1補助教授級生
活費及機票費
2請安排與中國
化學會會長見
面並在台北地
區增加一場演
講 7 John Ewart McGrady 9511 金必耀教授
量子化學計算化學 Professor of Computational Chemistry Univ of Glasgow UK
補助教授級生活
費及機票費
8 Hisao Nishiyama 95911-917 鄭建鴻教授
不對稱催化反應有機
合成 日本名古屋大學教授 補助教授級生活
費及機票費
9 Martin Head-Gordon 95129-1219 許昭萍博士
Theoretical Chemistry Electronic Structure Calculations
Professor Univ of California(Berkeley) USA
補助教授級生活
費及機票費
10 Masakatsu Shibasaki 951123-1129 王伯昌教授
生物有機有機合成
藥物化學 Professor The University of Tokyo Japan
補助教授級生活
費及機票費
- 7 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 11 Daniel G Nocera
951123-1129 王伯昌教授
奈米材料能源開發
電子轉移 Professor Massachusetts Institute of Technology USA
補助教授級生活
費及機票費
12Koichi Ohno 951121-26 游靜惠教授
Theoretical Chemistry Professor Tohoku University Japan
補助教授級生活
費及機票費
13Satoshi Yabushita 951121-26 游靜惠教授
Theoretical Chemistry Professor Keio University Japan
補助教授級生活
費及機票費
14 Laren M Tolbert 951119-26 陳建添教授
Organic photochemistryPhotobiology Electronic materials
Professor Associate Editor for the Journal of the American Chemical Society
補助教授級生活
費及機票費
(二) 同意推薦下列十位教授為國科會國際科技人士短期訪問教授生活費補助以不超
過七天為限並須給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Ann Mary Chippindale
95101-108 王素蘭教授
Solid State Chemistry Professor The University of Reading UK
補助教授級生活費及機票費
2 Steven Chu 951210-1216 倪其焜博士
物理應用物理 諾貝爾得主 Director Lawrence Berkeley National Laboratory USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 3 F Sherwood Rowland
951210-1216 倪其焜博士
Atmospheric Chemistry Chemical Kinetics
諾貝爾得主 Professor University of California Irvine USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶機票費
4 Dudley R Herschbach 951210-1216 倪其焜博士
Chemical Physics 諾貝爾得主 Professor Harvard University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 5J ohn B Fenn
951210-1216 倪其焜博士
Analytical chemistry 諾貝爾得主 Professor Virginia Commonwealth University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費
- 8 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 6 John C Polanyi
951210-1216 倪其焜博士
物理化學 諾貝爾得主 Professor Toronto University Canada
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 7 Chul-Ho Jun 951021-1027 鄭建鴻教授
催化反應金屬有機綠色化學
Professor Yonsei University Korea
補助教授級生活費及機票費
8 Nakeheol Jeong 951016-1021 陳竹亭教授
Organic Chemistry Professor Korea University Korea
補助教授級生活費及機票費
9 Hiroyuki Isobe 95111-116 陳竹亭教授
Organic Chemistry Associate Professor The University of Tokyo Japan
補助教授級生活費及機票費
10 Peter H Seeberger 95118-1113 洪上程教授
Organic Synthesis Carbohydrate Chemistry
Professor Eidgenossische Technische Hochschule Zurich Germany
補助教授級生活費及機票費
(三) 同意推薦下列研討會為國科會國際研討會
會 議 名 稱 建 議 補 助 經 費 備 註
1第八屆亞洲結晶學國際研討會 1200000 元
2 2006 年台灣生物無機研討會 560000 元
(四) 同意補助下列研討會經費如下
會 議 名 稱 補助金額 備 註
理論與計算化學研討會 49000 元 請檢據實報實銷
- 9 -
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
最 新 消 息
第 192 次(95629)中心審議會決議
(一) 同意推薦下列十四位教授為中心訪問教授生活費補助以不超過七天為限並須
給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Jean-Pascal Sutter
95101-109 鄭建中教授
Nano-porous architectures Molecule-based magnets Nano-magnets
法國Toulous(土魯士)國家化學研究院資深
研究員
補助教授級生活
費及機票費
2 Junji Inanaga 951018-1024 方俊民教授
鑭系金屬有機化學不
對稱及官能性有機合成
日本九州大學教授 補助教授級生活
費及機票費
3 Donald H Levy 951210-1216 劉國平教授
Laser spectroscopy in supersonic molecular beams
Professor the University of Chicago USA
補助院士級生活
費及機票費
4 Henry Shaefer 951210-1216 劉國平教授
理論化學 Professor the University of Georgia USA
補助院士級生活
費及機票費
5 John C Tully 951210-1216 劉國平教授
理論發展分子動力學 Professor Yale University USA
補助院士級生活
費及機票費
6 Thomas T Tidwell 951024-1030 宋光生教授
Destabilized carbocations Ketene chemistry Aromaticity and Antiaromaticity
Professor Univ of Toronto Canada President of Canadian Chemical Society
1補助教授級生
活費及機票費
2請安排與中國
化學會會長見
面並在台北地
區增加一場演
講 7 John Ewart McGrady 9511 金必耀教授
量子化學計算化學 Professor of Computational Chemistry Univ of Glasgow UK
補助教授級生活
費及機票費
8 Hisao Nishiyama 95911-917 鄭建鴻教授
不對稱催化反應有機
合成 日本名古屋大學教授 補助教授級生活
費及機票費
9 Martin Head-Gordon 95129-1219 許昭萍博士
Theoretical Chemistry Electronic Structure Calculations
Professor Univ of California(Berkeley) USA
補助教授級生活
費及機票費
10 Masakatsu Shibasaki 951123-1129 王伯昌教授
生物有機有機合成
藥物化學 Professor The University of Tokyo Japan
補助教授級生活
費及機票費
- 7 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 11 Daniel G Nocera
951123-1129 王伯昌教授
奈米材料能源開發
電子轉移 Professor Massachusetts Institute of Technology USA
補助教授級生活
費及機票費
12Koichi Ohno 951121-26 游靜惠教授
Theoretical Chemistry Professor Tohoku University Japan
補助教授級生活
費及機票費
13Satoshi Yabushita 951121-26 游靜惠教授
Theoretical Chemistry Professor Keio University Japan
補助教授級生活
費及機票費
14 Laren M Tolbert 951119-26 陳建添教授
Organic photochemistryPhotobiology Electronic materials
Professor Associate Editor for the Journal of the American Chemical Society
補助教授級生活
費及機票費
(二) 同意推薦下列十位教授為國科會國際科技人士短期訪問教授生活費補助以不超
過七天為限並須給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Ann Mary Chippindale
95101-108 王素蘭教授
Solid State Chemistry Professor The University of Reading UK
補助教授級生活費及機票費
2 Steven Chu 951210-1216 倪其焜博士
物理應用物理 諾貝爾得主 Director Lawrence Berkeley National Laboratory USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 3 F Sherwood Rowland
951210-1216 倪其焜博士
Atmospheric Chemistry Chemical Kinetics
諾貝爾得主 Professor University of California Irvine USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶機票費
4 Dudley R Herschbach 951210-1216 倪其焜博士
Chemical Physics 諾貝爾得主 Professor Harvard University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 5J ohn B Fenn
951210-1216 倪其焜博士
Analytical chemistry 諾貝爾得主 Professor Virginia Commonwealth University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費
- 8 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 6 John C Polanyi
951210-1216 倪其焜博士
物理化學 諾貝爾得主 Professor Toronto University Canada
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 7 Chul-Ho Jun 951021-1027 鄭建鴻教授
催化反應金屬有機綠色化學
Professor Yonsei University Korea
補助教授級生活費及機票費
8 Nakeheol Jeong 951016-1021 陳竹亭教授
Organic Chemistry Professor Korea University Korea
補助教授級生活費及機票費
9 Hiroyuki Isobe 95111-116 陳竹亭教授
Organic Chemistry Associate Professor The University of Tokyo Japan
補助教授級生活費及機票費
10 Peter H Seeberger 95118-1113 洪上程教授
Organic Synthesis Carbohydrate Chemistry
Professor Eidgenossische Technische Hochschule Zurich Germany
補助教授級生活費及機票費
(三) 同意推薦下列研討會為國科會國際研討會
會 議 名 稱 建 議 補 助 經 費 備 註
1第八屆亞洲結晶學國際研討會 1200000 元
2 2006 年台灣生物無機研討會 560000 元
(四) 同意補助下列研討會經費如下
會 議 名 稱 補助金額 備 註
理論與計算化學研討會 49000 元 請檢據實報實銷
- 9 -
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 11 Daniel G Nocera
951123-1129 王伯昌教授
奈米材料能源開發
電子轉移 Professor Massachusetts Institute of Technology USA
補助教授級生活
費及機票費
12Koichi Ohno 951121-26 游靜惠教授
Theoretical Chemistry Professor Tohoku University Japan
補助教授級生活
費及機票費
13Satoshi Yabushita 951121-26 游靜惠教授
Theoretical Chemistry Professor Keio University Japan
補助教授級生活
費及機票費
14 Laren M Tolbert 951119-26 陳建添教授
Organic photochemistryPhotobiology Electronic materials
Professor Associate Editor for the Journal of the American Chemical Society
補助教授級生活
費及機票費
(二) 同意推薦下列十位教授為國科會國際科技人士短期訪問教授生活費補助以不超
過七天為限並須給三場以上學術演講及繳交訪問報告 姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 1 Ann Mary Chippindale
95101-108 王素蘭教授
Solid State Chemistry Professor The University of Reading UK
補助教授級生活費及機票費
2 Steven Chu 951210-1216 倪其焜博士
物理應用物理 諾貝爾得主 Director Lawrence Berkeley National Laboratory USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 3 F Sherwood Rowland
951210-1216 倪其焜博士
Atmospheric Chemistry Chemical Kinetics
諾貝爾得主 Professor University of California Irvine USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶機票費
4 Dudley R Herschbach 951210-1216 倪其焜博士
Chemical Physics 諾貝爾得主 Professor Harvard University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 5J ohn B Fenn
951210-1216 倪其焜博士
Analytical chemistry 諾貝爾得主 Professor Virginia Commonwealth University USA
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費
- 8 -
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 6 John C Polanyi
951210-1216 倪其焜博士
物理化學 諾貝爾得主 Professor Toronto University Canada
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 7 Chul-Ho Jun 951021-1027 鄭建鴻教授
催化反應金屬有機綠色化學
Professor Yonsei University Korea
補助教授級生活費及機票費
8 Nakeheol Jeong 951016-1021 陳竹亭教授
Organic Chemistry Professor Korea University Korea
補助教授級生活費及機票費
9 Hiroyuki Isobe 95111-116 陳竹亭教授
Organic Chemistry Associate Professor The University of Tokyo Japan
補助教授級生活費及機票費
10 Peter H Seeberger 95118-1113 洪上程教授
Organic Synthesis Carbohydrate Chemistry
Professor Eidgenossische Technische Hochschule Zurich Germany
補助教授級生活費及機票費
(三) 同意推薦下列研討會為國科會國際研討會
會 議 名 稱 建 議 補 助 經 費 備 註
1第八屆亞洲結晶學國際研討會 1200000 元
2 2006 年台灣生物無機研討會 560000 元
(四) 同意補助下列研討會經費如下
會 議 名 稱 補助金額 備 註
理論與計算化學研討會 49000 元 請檢據實報實銷
- 9 -
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
姓名來訪日期及連絡人 主 要 專 長 現 職 備 註 6 John C Polanyi
951210-1216 倪其焜博士
物理化學 諾貝爾得主 Professor Toronto University Canada
1補助諾貝爾級生活費及機票費
2建議以同等待遇補助配偶
機票費 7 Chul-Ho Jun 951021-1027 鄭建鴻教授
催化反應金屬有機綠色化學
Professor Yonsei University Korea
補助教授級生活費及機票費
8 Nakeheol Jeong 951016-1021 陳竹亭教授
Organic Chemistry Professor Korea University Korea
補助教授級生活費及機票費
9 Hiroyuki Isobe 95111-116 陳竹亭教授
Organic Chemistry Associate Professor The University of Tokyo Japan
補助教授級生活費及機票費
10 Peter H Seeberger 95118-1113 洪上程教授
Organic Synthesis Carbohydrate Chemistry
Professor Eidgenossische Technische Hochschule Zurich Germany
補助教授級生活費及機票費
(三) 同意推薦下列研討會為國科會國際研討會
會 議 名 稱 建 議 補 助 經 費 備 註
1第八屆亞洲結晶學國際研討會 1200000 元
2 2006 年台灣生物無機研討會 560000 元
(四) 同意補助下列研討會經費如下
會 議 名 稱 補助金額 備 註
理論與計算化學研討會 49000 元 請檢據實報實銷
- 9 -
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
國科會化學推動中心補助學術研討會成果報告表
研 討 會 名 稱2006 國科會自然處化學分析小組第一次研討會 日 期九十五 年 二 月 二十五日 ( 星期六 ) 主 辦 單 位靜宜大學 舉 辦 地 點靜宜大學圖書館十樓蓋夏廳 連絡人及電話靜宜大學應用化學系 蔡素珍 教授 電話(04)26328001 轉 15205 郭秋君 助理 電話(04)26328001 轉 15023
丘秀華 秘書 電話(04)26328001 轉 11900 出席人數與會來賓與工作人員65人學生 100 人共計 165 人
會議經過及議程
2006 國科會自然處化學分析小組第一次研討會於民國九十五年二月二十五日
(星期六)假靜宜大學(圖書館十樓蓋夏廳)展開正式之議程本次研討會有兩大
主題『先進化學分析方法之發展』與『化學分析小組如何培育企業界所需之人才』
此次邀請到七位專家學者與傑出企業人士進行專題演講會中亦邀請專家學者與企業
領導人進行綜合座談(議程表如附件)
藉此會議分析小組成員進行下一任召集人選舉並開票選出中興大學化學系李茂
榮教授為下一屆分析小組召集人
大會於靜宜大學鄧嘉宏主秘與理學院張永和院長致歡迎詞後正式展開首先由東
方技術學院化妝品應用管理系孫昀妘助理教授主講The penetration of nanoparticle TiO2 in sunscreen products on skin 主要內容為探討化妝品防曬劑中TiO2粒子對於
皮膚穿透之影響由於TiO2會誘發細胞毒性因此本研究針對市售化妝品中之TiO2進行
定量工作研究中將市售化妝品塗敷於鴨蹼表面再利用石墨爐原子吸收光譜法來進
行TiO2之定量由研究結果顯示TiO2粒子越小對於皮膚之穿透性越佳並且殘留在皮
膚組織的時間也越長接下來的演講者為朝陽科技大學應用化學系陳政男助理教授
主要內容是利用NiCR(ClO4)2 所形成之離子訊號來探討 fused-droplet electrospary ionization mass spectrometry之離子化效能
茶敘後進行企業界美商奇異股份有限公司台灣分公司企業發展部李榮洲處長
演說主題為rdquo奇異公司需要何種高等教育人才rdquo在李處長的演講中可以明確知道
奇異公司需要具有創新獨立思考和能夠解決問題之人才由此演講教育界的朋友
可以有新的思維去培養專業的高等教育人才接下來的演講者為鈺德科技股份有限公
司張昭焚董事長張董事長站在企業界的觀點來探討企業界所需要的人才應具備哪些
條件和特質演講中提到包括對公司有向心力具備有好的外語能力和勇於嘗試的精
神等等
- 10 -
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
在兩場先進化學分析方法之發展與兩場化學分析小組如何培育企業界所需之人才後
進行『教育家與企業家的對談』提供業界學界與學生一個良好互動的機會經由
產學界的經驗交流使學生瞭解投入產業所需之條件瞭解目前整體產業的發展動
向讓學生對整個就業市場有更深入的了解有助學生瞭解自我的 SWOT 及就業方
向的選擇
午餐時間學者們進行學術交流與心得交換並恭賀中興大學李茂榮教授擔任下一屆
召集人餐敘後邀請國立師範大學化學系林震煌教授主講另一場精采的演講演講
主要內容為利用多頻雷射當作MALDI-TOFMS的離子源並進一步將此種分析技術應
用在毒品之檢測接著為國立中山大學化學系曾韋龍助理教授演講主要內容為利用
毛細管電泳和fluorescence imaging 系統偵測生物分子研究中利用charge-coupled device imaging 系統來觀察 λ-DNA 在 毛 細 管 中 的 遷 移 行 為 進 一 步 探 討
nanoparticle-filled 毛細管的分離機制接下來邀請國立師範大學化學系劉敏瑛助理教
授演講內容為利用毛細管區帶電泳分析人類血漿中之LDL particles在研究中並探
討LDL和LDL-在毛細管的遷移行為
最後為分析小組成員及專家進行之綜合座談最主要是讓分析小組成員因應國科會評
鑑標準方式的改變進行各項溝通會中決議請分析小組任國科會之諮議委員和審議委
員以及本組召集人決定合理之評估方法
綜而言之由研討會中之熱烈討論情形說明了此次研討會對於分析化學界之與
會學者人士與學生均具有相當的助益成效極為卓著分析小組成員與會期間經由溝
通與聯誼擴展視野了解分析化學現今之發展及研究新趨勢並可借彼此討論激盪現
有研究思維此次研討會與以往最大的不同點是邀請傑出企業界人士與會避免理論
與實務脫節更能培養出企業所需求的人才而讓學生畢業後無論升學或就業均
能學以致用畢業生除擁有分析化學之專業特長更能有宏觀的學養
此次研討會經費主要來自國科會化學推動中心與靜宜大學與會學生大部份是分析小
組成員所指導的研究生分析界親朋好有的支持無論是主持會議參加會議參加
座談會踴躍發言參加聯誼餐會都讓人很感激更感謝企業界朋友與靜宜大學校友的
經費贊助
靜宜大學的同仁以及同學在相關會議事務的努力與奉獻謹此亦一併致上最崇敬之謝
忱最後要感謝國科會給本人主辦此次研討會的機會做了一次成功的產學界交流
會議主持人 靜宜大學應用化學系 教授 蔡素珍 謹誌 20060320
- 11 -
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
附件一
議 程 表
日期九十五年 二 月 二十五日 ( 星期六 ) 地點靜宜大學圖書館十樓蓋夏廳
時 間 活動 主持人 演講貴賓
900 int
930
報到開幕 致歡迎詞
靜宜大學 俞明德 校長靜宜大學理學院 張永和 院長分析小組召集人 傅明仁 教授
930 int
1000 專題演講 台中榮總醫研部
陳甫州 主任
東方技術學院化妝品應用管理系 孫昀妘 助理教授 講題 The penetration of nanoparticle TiO2 in sunscreen products on skin
1000 int
1030 專題演講 國立中山大學化學系
江旭禎 主任
朝陽大學應用化學系 陳政男 助理教授 講題 The studies of formation of non-oxidative macrocyclic nickel complexes ions in electrospray ionization source
1030 int
1100 茶敘
1100 int
1130 專題演講 國立中興大學化學系
曾志明 教授
美商奇異股份有限公司台灣分公司企業發展部李榮洲 處長 講題 奇異公司需何種高等教育人才
1130 int
1200 專題演講 國立台灣大學化學系
何國榮 教授
鈺德科技股份有限公司 張昭焚 董事長 講題 企業界需何種高等教育人才
1200 int
1300
教育家與 企業家對談
國立清華大學原科系
楊末雄 教授
鈺德科技股份有限公司 張昭焚 董事長
引言人國立中興大學化學系 鄭政峰 教務長 引言人國科會自然處
瞿港華 教授 引言人國立交通大學應用化學系
李耀坤 主任 引言人美商奇異台灣分公司
企業發展部李榮洲 處長
1300 int
1400 午餐
- 12 -
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
時 間 活動 主持人 演講貴賓
1400 int
1430 專題演講
國立成功大學化學系 陳淑慧 教授
國立台灣師範大學化學系 林震煌 教授 講題 Development of multi-frequency laser for the use in MALDI-TOFMS
1430 int
1500 專題演講
國立中興大學化學系 李茂榮 教授
國立中山大學化學系 曾韋龍 助理教授 講題 Determination of biomolecules by capillary electrophoresis and fluorescence imaging system
1500 int
153 0 專題演講
國立臺灣大學化學系 張煥宗 教授
國立彰化師範大學大學化學系 劉敏瑛 助理教授 講題 Charge density profiling of circulating human low-density lipoprotein particles by capillary zone electrophoresis
1530 int
1630 综合座談
分析小組召集人 東吳大學化學系 傅明仁 教授
1700 聯誼餐會
東籬農園 台中市西屯區西平南巷 6-6
號 (福林路底) 04-24656888
- 13 -
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
國科會化學推動中心補助學術研討會成果報告表
會議名稱2006 年無機錯鹽小組學術研討會
舉辦日期民國 95 年 4 月 28 日
主辦單位國科會化學推動中心(無機錯鹽小組)
協辦單位中山大學理學院中山大學化學系
承 辦 人梁蘭昌
舉辦地點中山大學理學院小劇場
聯絡電話Tel (07) 5252000 x 3945 Fax (07) 5253908
出席人數 142 人
會議經過及議程
2006 年無機錯鹽小組研討會於民國九十五年 4 月 28 日(星期五)假中山大學理
學院小劇場舉行本次研討會邀請到十位在無機化學相關領域之教授擔任講座(議程
表如附件)
研討會報到及正式開始時間為上午 0850程序開始首先由中山大學化學系董騰元
教授主持第一部份的會議而第一場演講於 0855-0930 東吳大學化學系王志傑教授
主講演講的題目為 Assemblies of Metal-Coordination Frameworks Constructed by
Croconate and Pyridyl-containing Ligand其主要內容的重點如下
During the past years the bonding characteristics of croconate (C5O52- dianion of
45-dihydroxycyclo-pent-4-123-trione) with first transition metal ions and some
complexes of croconate associated with another co-ligand have been widely investigated
and show that this cyclic oxocarbon ligand can be coordinated to the metal ions using
various bonding modes The versatile structural topologies of MOFs depend both on the
selection of the coordination geometry of metal centers and coordination behavior of the
croconate ligands In the present study four types of coordination polymers with
interesting 1D and 2D MOFs constructed by croconate bridges associated with N-based
ligands will be described as following
1 1D linear or zigzag chains of [M(C5O5)(H2O)2](Cu(en)2) (M = Mn Co Ni Cu Zn) via
the bridges of croconate with bidentatemonodentate micro123- micro124- and bismondentate
micro13-coordination modes
2 2D layer [Cd2(L)(C5O5)2(H2O)]infin (L = 44rsquo-bipyridine (bpy) and
12-bis(4-pyridyl)ethane (dpe)) with two rectangle boxes as the basic building units via
- 14 -
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
the bridges of croconate with bis-bidentate adjacent micro3- and the
bidentatethree-adjacent micro5-coordination modes and L ligand
3 2D bilayer [M2(L)2(C5O5)2]sdotnH2Oinfin (M = Mn Fe Co Cd L =
12-bis(-4-pyridyl)ethane) (dpe) M = Ni Co Zn L = 12-bis(-4-pyridyl)ethylene)
(bpe)) with a rectangle grid as the basic building unit via the bridges of croconate with
bis-bidentate adjacent micro3- and micro4-coordination modes and L ligand
4 2D layer [Cd(C5O5)(bpym)05(H2O)] with Cd3 and Cd4 skeletons as the basic building
units via the bridges of bis-bidentatemonodentate micro5-coordination modes and bpym
ligand
O
O
O
O
O
MM
O
O
O
O
O
M
M
O
O O
O O
MM
micro123-coordination mode micro124-coordination mode micro13-coordination mode
O
O O
O O
M M
O
O O
O OMM
O
O O
O O
M M
M
- 15 -
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
O
O O
O OMM
M
bis-bidentate
adjacent micro3-
bis-bidentate
adjacent micro4-
bidentate
three-adjacent micro5-
bis-bidentatemonodentate
micro5-
而 0930-1005 的演講由高雄大學應用化學系李頂瑜教授主講演講的題目為
An Efficient System of Controlled Radical Polymerization and Its Application其主要內
容的重點如下
Photolithography has been and will be the technological basis in semiconductor
industry In this technology one of key materials keeping lines smaller and smaller is
photoresists of which one of the major components is polymer As the line width goes
down smaller the quality of the photoresist polymer demands higher Therefore
well-defined polymer needs to be prepared
In use of S-cyanoprop-2-yl-S-methyl trithiocarbonate (MeS(C=S)SC(CN)Me2) as a
mediator in reversible addition-fragmentation chain transfer (RAFT2) polymerization
random tert-butyl acrylate-acetoxystyrene copolymer block tert-butyl
acrylate-acetoxystyrene copolymer random tert-butyl acrylate-acetoxystyrene-styrene
copolymer and block tert-butyl acrylate-acetoxystyrene-styrene copolymer were
synthesized After deprotection of the acetoxy group the analogous copolmers of
hydroxystyrene were obtained Lithographic evaluation for 248 nm exposure showed
the patterning performance of the random tert-butyl acrylate-hydroxystyrene copolymer
(Fig1 (a)) was better than that of block tert-butyl acrylate-hydroxystyrene-styrene
copolymer (Fig1 (b))
Figure 1 (a) Figure 1 (b)
- 16 -
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
1005-1040 的演講由台灣師範大學化學系李位仁教授主講演講的題目為
Conversion of Acetonitrile to Thioimino Acetate on Tris(2-mercaptophenyl)phosphine of
Nickel Complexes其主要內容的重點如下
Nitriles are toxic to all living systems Fortunately nature has a way to convert
aromatic and aliphatic nitriles to less toxic corresponding acids and ammonia directly by
nitrilases or by nitrile hydratases and subsequently amidases A similar conversion was
observed in the reaction of [Ni(CH3CN)6](ClO4)2 with P(o-C6H4SH)3 or
P(C6H5)(o-C6H4SH)2) in acetonitrile The resulting yellow brown complexes of
[Ni(P(C6H4S)(C6H4SC(CH3)NH2)2)2](ClO4)4 and [Ni(P(C6H4S)(C6H5)(C6H4S-
C(CH3)NH2)2)(ClO4)2 were characterized by X-ray diffraction analysis The structures of
the obtained complexes revealed the conversion of the thiophenol on the phosphine
ligaends to thioimino acetate Under the same reaction condition the similar conversion
was not observed in the reaction of P(o-C6H4SH)3 and HClO4 in acetonitrile However
P(o-C6H4SH)3 would convert to [P(o-C6H4SH)2(C6H4SC- (CH3)NHCOCH3)] after the
reaction mixture underwent for 30 days These results suggested the conversion of
acetonitrile to thioimino acetate was accelerated with the assistance of a Lewis acidic
Ni(Ⅱ) ion
1040-1050 為休息時間接下來第二部份的會議由東華大學化學系劉鎮維教授
主持而 1050-1125 的演講由中央研究院化學研究所林建村教授主講演講的題目
為有機金屬在光電材料上的應用其主要內容的重點如下
藉由三個系列光電材料本報告討論有機金屬可以扮演的角色(1)藉由配基的改
變可以調變系列銥金屬有機錯合物之磷光光色包括紅橘黃綠部份化合物
並可製成高效能之電激發光元件(2)利用鈀金屬化合物催化碳-碳或碳-氮鍵之生成
包括 Stille cross-coupling Suzuki coupling Hartwigrsquos reaction 等可得到系列雙極性化
合物這些化合物可以利用為光敏劑並製成高效率之光敏型太陽能電池(2)利用
鈀金屬化合物催化碳-碳或碳-氮鍵之生成包括上述反應與 Sonogashira coupling
reaction 等 可得到系列具雙光子吸收之化合物這些化合物屬 quadrupolar 型並
具有不錯的雙光子吸收 cross section 值
1125-1200的演講由暨南國際大學應用化學系林敬堯教授主講演講的題目
Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial
Electron-Transfer on TiO2 Nano-crystalline Films其主要內容的重點如下
The synthesis electrochemistry AFM UV-visible absorption static and ultrafast
- 17 -
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
fluorescence studies of a series of carboxyphenylethynyl zinc porphyrins ZnCA(PE)nBPP
(n = 1-4) were reported These porphyrins were synthesized in order to study the
interfacial electron-transfer reactions on the TiO2 nanocrystalline surfaces The distances
between the porphyrin core and the anchoring carboxylic group were controlled by the
(phenylethynyl)n bridging groups The UV-Visible absorption fluorescence and
electrochemical studies showed that the properties of the porphyrin core were not greatly
perturbed by the substituents More importantly the AFM images and the absorption
spectra of these macrocycles on the TiO2 nanocrystalline films suggested that the
porphyrins were orderly attached onto the TiO2 nanocrystalline surfaces in the
H-aggregation fashion
1200-1350 為午餐兼學術交流時間下午第三部份的會議於 1450 開始由清
華大學化學系廖文峰教授主持而 1355-1430 的演講由中央大學化學系李光華教授
主講演講的題目為 High-Temperature High-Pressure Hydrothermal Synthesis of Metal
Silicates其主要內容的重點如下
Recently much work has focused on the synthesis of transition metal silicates because of
their rich structural chemistry and interesting physical and chemical properties A good
number of vanadium silicates have been synthesized Some of them show good thermal
stability absorption and ion-exchange properties Most of these compounds were
synthesized with alkali metal cations under hydrothermal conditions at 180-240 degC A
uranium and a niobium silicate have also been synthesized by using organic ammonium
templates Our synthetic methods are 2-fold namely high-temperature high-pressure
hydrothermal reactions in gold ampoules contained in a high-pressure reaction vessel at ca
550-600 ordmC and 1000-2000 bars with alkali metal counter cations and molten flux reactions
in a platinum crucible at high temperature We have synthesized a large number of new
silicates of transition metals main group elements lanthanides and uranium For example
we reported the synthesis of Rb4(NbO)2Si8O21 and its solid-state NMR spectra The 29Si
- 18 -
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
MAS NMR spectrum shows multiplet patterns which arise from 93Nb(spin-92)-29Si
J-coupling This is the first example of two-bond J-coupling between a quadrupolar
nucleus and a spin-12 nucleus in the solid state The structure Rb3In(H2O)Si5O13 consists
of 5-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to
four adjacent 5-membered rings to form a 3D silicate framework which belongs to the
CdSO4 topological type The structure is related to that of the titanium silicate ETS-10 and
they are the only two metal silicates which have the CdSO4 topological type structure The
first pentavalent-uranium silicate has also been synthesized In this presentation I will
report the syntheses crystal structures solid-state NMR spectroscopy and properties of a
number of new metal silicates
而 1430-1505 的演講由清華大學化學系黃暄益教授主講演講的題目為
Shape-Controlled Synthesis of Gold Nanostructures其主要內容的重點如下
Recently there is a growing interest in preparing anisotropic gold nanostructures such as
nanorods and nanoplates Syntheses of branched gold nanocrystals high aspect ratio gold
nanorods and triangular and hexagonal gold nanoplates are presented Branched gold
nanocrystals were prepared by a seeding growth approach The highly faceted
nanoparticles grown from the gold seeds (~2ndash4 nm in diameter) then transformed into
branched nanocrystals (~40 nm in length) by further addition of the SDSndashHAuCl4 solution
and ascorbic acid for particle growth High aspect ratio gold nanorods were also
synthesized by the seed-mediated approach Nitric acid was added during nanorod growth
to significantly enhance the production of high aspect ratio gold nanorods The resulting
nanorods have uniform diameters of 19ndash20 nm and can reach lengths of 400ndash500 nm to
yield nanorods with average aspect ratios of 21ndash23 The synthesis of gold nanoplates was
carried out in aqueous solution by thermal reduction of HAuCl4 with trisodium citrate in
the presence of CTAB surfactant in just 5ndash40 min The sizes of the gold nanoplates can be
varied from as small as tens of nanometers in width to several hundreds of nanometers
and even a few microns in width by changing the reagent concentrations solution
temperature and the reaction time Inorganicndashorganic hybridized nanomaterials may be
prepared using these anisotropic gold nanostructures through surface functionalization
1505-1515 為休息時間接下來第四部份的會議由成功大學化學系許拱北教授
主持而 1515-1550 的演講由清華大學化學系蔡易州教授主講演講的題目
Low-Coordinate and MultiplyminusBonded MminusM Complexes其主要內容的重點如下
Binuclear complexes of M2[DippNSi(Me)2NDipp]2 in which M is Mo W Mn or Zn
DippNSi(Me)2NDipp is a bidentate diamide ligand and Dipp stands for 26-i-PrC6H3 will
- 19 -
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
be presented When M is Mo 1 or W 2 both compounds possess two
bis(phenylamido)dimethylsilane ligands DippNSi(Me)2NDipp spanning a metalminusmetal
quadruple bond and consequently forming a fused bicyclic skeleton The metric of the
metalminusmetal bond distances is 21784(12) and 22845(7) Aring for 1 and 2 respectively which
are considered slightly long quadruple bonds Sophisticated density functional theory (DFT)
calculations indicate the bonding is different tha n that in Cottonrsquos paddlewheel motifs
As for binuclear Mn2 and Zn2 complexes the ligation of DippNSi(Me)2NDipp varies with
the change of the oxidation state of Mn2 cores Mn2[DippNSi(Me)2NDipp]2 3 for example
displays a ldquocyclooctadiene likerdquo structure featuring a nonplanar MnNMnN core The
diamide ligand is both chelating and bridging so that one of the nitrogen is three-coordinate
and the other four-coordiante However addition of one electron to 3 results in a structural
rearrangement from ldquocyclooctadiene likerdquo structure to a fused bicyclic skeleton
[Mn2(DippNSi(Me)2NDipp)2]- 4 reminiscent of that of 1 and 2 The bond length between
Mn atoms is 26851(9) Aring Compound 4 shows an antiferromagnetic interaction between
the two Mn centers Interestingly addition of one more electron to 4 induces
(DippNSi(Me)2NDipp) chelation to one Mn atom and a MnminusMn bond (2742(4) Aring)
forming [(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]2- 5 Removal of one
electron on the other hand from 3 generates
[(DippNSi(Me)2NDipp)MnMn(DippNSi(Me)2NDipp)]+ 6 whose structure resembles that
of 5 and the distance between two Mn centers is 27456(13) Aring The variation in structure
between complexes 3 4 5 and 6 also occurs to Zn Complex Zn2[DippNSi(Me)2NDipp]2
7 exhibits a structure reminiscent of that of complexes 1 2 and 4 while two-electron
reduction of 7 yields [(DippNSi(Me)2NDipp)ZnZn(DippNSi(Me)2NDipp)]2- 8 featuring a
ZnminusZn bond of 23643(11)Aring
而 1550-1625 的演講由中興大學化學系陳如珍教授主講演講的題目為
Symmetry and Bonding in Metalloporphyrins-Symmetry Switch in Nature其主要內容的
重點如下
近年來愈來愈多的證據顯示非平面鐵卟啉普遍存在血紅素蛋白中可能是控制其
生物功能的一種重要機制因此非平面金屬卟啉的研究逐漸受到重視結合 NMR 光
譜與理論計算仔細分析五配位和六配位高自旋三價鐵卟啉中對稱改變對鍵結所造成
的影響
在本次演講的主題即延續上述工作進一步探討大環變形對五配位和六配位高自
旋三價鐵卟啉對稱與鍵結的影響並評估其電子組態可能的變化在五配位系統中我
- 20 -
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
們選擇平面型Fe(TPP)Cl馬鞍型Fe(OETPP)Cl和皺摺型Fe(TiPP)Cl進行分析其中
dz2-a2u的鍵結作用普遍存在上述三種結構但在馬鞍型變形系統中a2u同時可與dx2-y
2
dz2作用a1u可與dxy作用dx
2-y
2能量上升大於dxy使Fe(OETPP)Cl呈現量子混合中自
旋(S = 3252)電子組態皺摺變形a2u同時可與dxy dz2作用dx
2-y
2對稱雖與a1u相同
但幾乎沒有作用故Fe(TiPP)Cl仍保持高自旋狀態在皺摺系統的分析中我們同時利
用計算驗證在NMR光譜中所觀察到的超共軛現象我們選擇THF六配位系統
[Fe(TPP)(THF)2]+[Fe(OETPP)(THF)2]+和[Fe(TiPP)(THF) 2]+以高自旋狀態進行類似的
鍵結分析和光譜比對其中除了dz2-a2u的鍵結作用消失之外其他的軌域對成語鍵結
作用都和五配位系統相同特別值得一提的是在馬鞍型變形環境下dxy與a1u的作用
比在皺摺環境下dxy與a2u的作用更強而dx2
-y2-a2u與dx
2-y
2-a1u的作用在馬鞍型環境下很
重要在皺摺型環境下卻發揮不了影響使得[Fe(OETPP)(THF)2]+ 更有機會呈現不
尋常的(dxzdyz)3(dxy)1(dz2)1中自旋電子組態這個結論顯然與M Nakamura et al最近發
表在JACS的結果相反此外對於具有擴大π電子系統的四苯基四苯卟啉 (TPTBP)在
合成純化上獲得關鍵的進展並藉由meso-13C的標示完全確認Fe(TPTBP)Cl的13C
NMR光譜配合理論計算與鍵結分析我們得到一個很有趣的結論Fe(TPTBP)Cl
的電子組態符合高自旋三價鐵S = 52 的狀態但其中dxy與a1u以接近 50 的鍵結作
用突顯其未偶電子之非定域化使其呈現部分FeⅡP+bullCl的性質符合TBP擴大電子
系統較易氧化的特性
另外近年來紫質相關的研究顯示非平面紫質廣泛存在生物系統中因此大環變
形對血紅素蛋白生物功能的影響自然成為一個新興的研究重點根據先前的研究結果
顯示五配位三價鐵卟啉大環呈現馬鞍型變形因此降低其配位環境的對稱性(C4v rarr
C2v)一方面增加金屬與卟啉間鍵結作用的數目使dx2-y2軌域能量上升穩定中自
旋產生中自旋電子組態另一方面導致dx2
-y2與dz
2軌域發生強烈的混成造成鍵結
的方向性這種鍵結的方向性很可能是影響電子傳遞速率的重要機制於是我們提出
〝對稱開關〞的概念
我們當初根據磁矩77 K測得之EPR光譜以及Fe-Np鍵長和理論計算等方法估算
Fe(OETPP)Cl為量子混合中自旋(S = 52 32)的電子組態其中高自旋和中自旋的
貢獻分別為 60 和 40 1999 年Weiss等人根據 4 K EPR和Moumlssbauer光譜於Angew
Chem提出不同的看法認為Fe(OETPP)Cl之中自旋貢獻應少於 10 為了進一步
澄清這個疑點我們採取的策略是藉由軸配基強度的調整希望能夠找到接近純的高
- 21 -
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
自旋和中自旋的Fe(OETPP)X錯化物經由1H NMR13C NMR和EPR磁矩的測量
結構的分析再配合理論的計算重新估算Fe(OETPP)Cl的電子組態我們同時也對
Fe(OMTPP)X系列做了類似的研究此外為了進一步證實在變形金屬卟啉中鍵結方
向性的問題我們試著從上述Fe(OETPP)X及Fe(OMTPP)X系列錯化物之1H NMR和13C
NMR光譜分析其中經由鍵結方向性所產生之自旋密度的差異性
1625-1700 的最後一場演講是由中央研究院化學研究所江明錫教授主講演講
的題目為 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates其主要內容的
重點如下
X-ray absorption spectroscopy was successfully used to probe 5f-ion speciation in the
Wells-Dawson (WD) and Preyssler (PA) anionic complexes The coordination environment
of the 5f-ion showed similarity with that of the 4f-ion in both metal-oxide fragments The
An ions were bridged by 8 oxo-groups to the tungsten centers Changes on the bond
distances were mainly influenced by ionic radii of the f ions in the proportional manner
indicating the major interaction between the 5f ions and the oxotungsates was in dipolar
character This force also played an important role on changes of the spectroscopic and
redox properties In-situ spectroelectrochemistry provided a direct route to disentangle
overlaps of the redox responds from the f ions and d states Different Nernstian results in
Np- and Pu-WDs and unusual correlated electron behavior in Eu-PA could be explained by
individual frontier molecular orbital diagrams
會議於 1705 圓滿結束此次會議人員參與踴躍並由會中之熱烈討論情形說明
了此次研討會對於與會學者均具有明顯的助益此次研討會承蒙國科會自然處化學中
心經費資助中山大學理學院中山大學化學系協助特此致謝擔任講座教授及服
務同學在此一並致謝
- 22 -
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
與會老師合影
- 23 -
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
- 24 -
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
2006 年無機錯鹽小組研討會 時間 2006 年 4 月 28 日 (星期五)
地點 中山大學化學系 0850 研討會開始 Chair 董 騰 元教授 (中山大學化學系) 0855 ndash 0930 王 志 傑 教授 (東吳大學化學系)
講題 Assemblies of Metal-Coordination Frameworks Constructed by Croconate and Pyridyl-containing Ligands
0930 ndash 1005 李 頂 瑜 教授 (高雄大學應用化學系) 講題 An Efficient System of Controlled Radical Polymerization and Its
Application 1005 ndash 1040 李 位 仁 教授 (台灣師範大學化學系)
講題 Nickel Induced Conversion of Acetonitrile to Thioimino Acetate on Tris (2-mercaptophenyl) phosphine
1040 ndash 1050 Coffee and Tea break Chair 劉 鎮 維 教授 (東華大學化學系) 1050 ndash 1125 林 建 村 教授 (中央研究院化學研究所)
講題 有機金屬在光電材料上的應用 1125 ndash1200 林 敬 堯 教授 (暨南國際大學應用化學系)
講題 Designing Distance-Controlled Porphyrin-Based Photosensitizers for Studying Interfacial Electron-Transfer on TiO2 Nano-crystalline Films
1200 ndash 1350 午餐時間 兼 學術交流 Chair 廖 文 峰 教授 (清華大學化學系) 1355 ndash 1430 李 光 華 教授 (中央大學化學系) 講題 Synthesis and Structures of Metal Silicates 1430 ndash 1505 黃 暄 益 教授 (清華大學化學系)
講題 Shape-Controlled Synthesis of Gold Nanostructures 1505 ndash 1515 Coffee and Tea break Chair 許 拱 北 教授 (成功大學化學系) 1515 ndash 1550 蔡 易 州 教授 (清華大學化學系)
講題 Low-Coordinate and Multiply Bonded Metal-Metal Complexes 1550 ndash 1625 陳 如 珍 教授 (中興大學化學系)
講題 Symmetry and Bonding in Metalloporphyrins - Symmetry Switch in Nature 1625 ndash1700 江 明 錫 教授 (中央研究院化學研究所)
講題 f-ion Speciation and d-f Interaction LnAn-Polyoxotungstates 1700 ndash 1705 Closing remarks 主辦單位 國科會化學研究推動中心 (無機錯鹽小組) 承辦單位 中山大學化學系 聯 絡 人 梁蘭昌 [Tel (07) 5252000 x 3945 Fax (07) 5253908]
- 25 -
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
訪問教授訪問報告表
姓名Kazuhiko Nakatani 教授
訪問日期民國 2006 年 03 月 05 日 至 民國 2006 年 03 月 10 日
接待機構 國立臺灣師範大學化學系 接待人陳建添 教授 聯絡電話 29309095
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過 Nakatani 教授在 03 月 5 日﹝星期日﹞晚上 8 時 20 分抵達桃園中正國際
機場在臺師大陳建添 教授陪同下直抵中信商務會館然後直接 check-in休息到片刻
後我陪同他到我實驗室參觀並和他討論我們實驗室的研究成果3 月 6 日﹝星期一﹞
早上 9 點 30 分由我-臺灣師範大學化學系陳建添 教授接待首先安排與謝明惠 系主
任作簡短會晤並系上介紹後由李位仁 教授作研究交流與討論隨後再與我作研究
交流與討論中午與系上老師在福華文教會館餐敘後在 2 點 10 分第一場專題演講
演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物
經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進行定序選擇性鍵結從其定序選擇
性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定量其定序選擇性的效率接著他也
利用此技術來選擇性鍵結染色體 DNA 末端 telomere 的 GGC 重覆序列演講之後與陳
錕銘葉名倉等教授作研究交流與討論隨後與系上老師用完晚餐後結束拜訪行程
3 月 7 日﹝星期二﹞在 11 點左右到達新竹交通大學應用化學系首先由李旭琨 教授接
待做簡短會晤後中午與系上老師餐敘隨後開始進行第二場專題演講演講主題
為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺
旋 DNA 中 Guanine-Guanine 等 matched 序列進行定序選擇性鍵結將其固定於金奈
米粒子上藉由其定序選擇性鍵結後表面電漿共振強度的變化來定量其定序選擇性的
效率接著參觀生化所然後與鍾文聖刁維光教授作研究交流與討論隨後與系上老
師用完晚餐後結束拜訪行程3 月 10 日﹝星期五﹞早上 9 點半由臺灣大學化學系陸天堯
教授接待首先與牟中原 系主任作短暫的 30 分鐘會晤之後與陳昭岑 教授作研究交
流與討論中午與系上老師午餐餐敘後下午 2 點與陸天堯教授作研究交流與討論在
3 點半左右作第三場專題演講演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列進
行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來定
量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體 DNA 末端 telomere的 GGC 重覆序列演講之後與羅禮強陳竹亭等教授作研究交流與討論隨後與系
上老師用完晚餐後結束拜訪行程03 月 11 日﹝星期六﹞早上搭機返回大阪
- 26 -
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
2 演講行程及概要
3 月 6 日﹝星期一﹞下午 2 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 月 7 日﹝星期二﹞下午 2 點 10 分 演講主題為rdquoLigands binding to Mismatched Base Pairs Design and Application to the SNP Typingrdquo 主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 等衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 等matched 序列進行定序選擇性鍵結將其固定於金奈米粒子上藉由其定序選擇性鍵
結後表面電漿共振強度的變化來定量其定序選擇性的效率
3 月 10 日﹝星期五﹞下午 3 點 10 分 演講主題為Small Molecular Ligands binding to the Repeat DNA Sequence Telomere and CXG repeats主要涵蓋如何以一些 Naphthyridine Carbamate 和 Ureidoquinoline 衍生物經由與雙股螺旋 DNA 中 Guanine-Guanine 序列
進行定序選擇性鍵結從其定序選擇性鍵結後 DNA 的 UV 吸收與熔點變化的大小來
定量其定序選擇性的效率接著他也利用此技術來選擇性鍵結染色體DNA末端 telomere的 GGC 重覆序列
3 重要收獲及心得
對於不對稱掌性生化有機奈米生化材料跨領域研究將有更深入的另一層次的啟發
提供跨領域研究成功模式的利基效益與經驗對照參考從而效法並修正成為適合臺
灣進行跨領域研究的範本
4 其他意見
無
- 27 -
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
訪問教授訪問報告表(Visiting Report)
姓名Wayne L Gladfelter
訪問日期民國 95 年 3 月 11 日 至 民國 95 年 3 月 18 日
接待機構中正大學化學暨生物化學系 接待人 吉凱明 聯絡電話05-2428128
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Gladfelter 教授目前為明尼蘇達大學 IT Distinguished Professor去年底剛卸下化學
系主任的職務其為國際知名之化學氣相沉積(CVD)與固態材料化學專家他於 3月 11 日下午抵台訪問停留台灣期間赴中央研究院化學所中正大學化學暨生
物化學系清華大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 311 (星期六) 傍晚抵達台灣 312 (星期日) 前往嘉義阿里山觀光 313 (星期一) 下午拜訪中正大學並與羅仁權校長晤談 314 (星期二) 拜訪中正大學化學暨生物化學系並發表演講與討論 315 (星期三) 拜訪台灣大學化學系並發表演講與討論 316 (星期四) 拜訪中央研究院化學研究所並發表演講與討論 317 (星期五) 參觀中央銀行鑄幣廠及故宮博物院
與明尼蘇達大學化學系在台系友晚餐 318 (星期六) 離台
3重要收獲及心得
Gladfelter 教授在台演講內容主要是有關組合式化學氣相沉積 (combinatorial CVD)複合金屬或金屬氧化物薄膜方面的研究是藉著調控 CVD 反應參數在一次製程
中獲得不同組成之產物並使用精密之表面分析技術及物性量測決定最佳之 CVD製備條件這是一項極新的化學氣相沉積技術他在中正大學及中央研究院化學
研究所演講題目為 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates於清華大學演講題目為 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides附件為其演講內容之摘要 縱觀 Gladfelter 教授本次之訪問帶來新的化學氣相沉積技術知識多項先進的表面
分析方法以及電子元件最新製程經由其此次之訪問將有助於國內學者對於化
學氣相沉積之瞭解
4其他意見
Gladfelter 教授除了是知名的無機材料化學學家在固態表面分析技術的專研極深曾擔
任明尼蘇達大學材料分析儀器中心副主任此次來訪在如何利用跨領域知識解決重
要科學問題上對我們有極重要的啟發及示範同時Gladfelter 教授擔任化學系主任六
年對於如何提昇大學化學教育及加強國際學術交流方面亦提供許多寶貴意見
- 28 -
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
Attachment The abstract of Prof Wayne L Gladfelterrsquos talk Title 1 Combinatorial Chemical Vapor Deposition and Atomic Layer Deposition of Nanolaminates Abstract
The presentation outlined two topics For the first a low-pressure chemical vapor
deposition (CVD) reactor was modified to produce a continuous compositional spread of
titanium tin and hafnium dioxides on a single Si(100) wafer The corresponding
anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4 were used as single-source
precursors to the component oxides The compositions were mapped using X-ray
photoelectron spectroscopy and Rutherford backscattering spectrometry On a single
wafer an array of 100 microm x 100 microm capacitors was used to map the effective dielectric
constant (κeff) of the films For compositional spreads grown at 400 and 450 degC κeff
reached a maximum value in regions with the highest concentrations of TiO2 The
formation of the orthorhombic α-PbO2 phase for a composition near Hf075Sn025O2 was
also observed in the 450 degC compositional spread This combinatorial approach to
materials synthesis provided a high-throughput approach to 1) the optimization of physical
properties 2) the discovery of new materials and 3) the discovery of new deposition
chemistry
Atomic layer deposition (ALD) is emerging as an important thin film deposition
technology that can impact diverse fields including microelectronics optical coatings and
catalysis The method involves sequential exposure of a substrate to two molecular
precursors that when combined form a solid state film During exposure of the surface to
the first precursor specific groups are reacted and a fragment of the precursor remains
bound to the surface The second precursor reacts with this fragment to form the desired
film and regenerate the starting surface The cycle is repeated as many times as necessary
to generate the target thickness Although it is a slow deposition process it is without peer
in its ability to coat complex shapes uniformly with sub nanometer precision in thickness
Nanolaminates of HfO2 and SiO2 were prepared using atomic layer deposition methods
Successive exposure of substrates maintained at 120 or 160degC to nitrogen flows containing
Hf(NO3)4 and (tBuO)3SiOH led to typical bilayer spacings of 21 nm with the majority of
this being SiO2 As long as the precursors were allowed to saturate the surface this
reproducible thickness was controlled entirely by the precursor chemistry The density of
the SiO2 layers (measured using X-ray reflectometry) was slightly higher than expected for
amorphous silica suggesting that as much as 10 HfO2 was incorporated into the silica
- 29 -
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
layers Based on cross-sectional TEM (Figure 1) and X-ray reflectometry oxidation of the
silicon substrate was observed during its first exposure to Hf(NO3)4 leading to a SiO2
interfacial layer and the first HfO2 layer Combining the Hf(NO3)4(tBuO)3SiOH ALD with
ALD cycles involving Hf(NO3)4 and H2O allowed the systematic variation of the HfO2
thickness within the nanolaminate structure This provided an approach towards
controlling the dielectric constant of the films The dielectric constant was modeled by
treating the nanolaminate as a stack of capacitors wired in series The nanolaminate
structure inhibited the crystallization of the HfO2 in post-deposition annealing treatments
As the HfO2 thickness decreased the preference for the tetragonal HfO2 phase increased
Title 2 Combinatorial Chemical Vapor Deposition of Multimetallic Metal Oxides Abstract
The combinatorial approach to
materials synthesis provides a
high-throughput approach to 1) the optimization of physical properties 2) the discovery of
new materials and 3) the discovery of new deposition chemistry This presentation provides
several examples of a new process called combinatorial chemical vapor deposition A
low-pressure chemical vapor deposition (CVD) reactor was modified to produce a
continuous compositional spread of titanium tin and hafnium dioxides on a single Si(100)
wafer The corresponding anhydrous metal nitrates Ti(NO3)4 Sn(NO3)4 and Hf(NO3)4
were used as single-source precursors to the component oxides The compositions were
mapped using X-ray photoelectron spectroscopy and Rutherford backscattering
spectrometry On a single wafer an array of 100 microm x 100 microm capacitors was used to
map the effective dielectric constant (κeff) of the films For compositional spreads grown
at 400 and 450 degC κeff reached a maximum value in regions with the highest concentrations
of TiO2 The formation of the orthorhombic α-PbO2 phase for a composition near
Figure 1 Cross-sectional TEM of a HfO2SiO2 nanolaminate deposited by ALD The scale bar represents 1 nm
- 30 -
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
Hf05Sn05O2 was also observed in the 450 degC compositional spread Similar results were
obtained for the ZrO2-HfO2-SnO2 system
A second study focused on developing an approach to amorphous films of HfO2 (and
ZrO2) and SiO2 that are of interest as replacements for the SiO2 gate dielectric in field
effect transistors Tri(t-butoxy)silanol was chosen as the SiO2 precursor whereas the
anhydrous metal nitrates of hafnium and zirconium were used as the source of HfO2 and
ZrO2 Simultaneous injection of the silanol and nitrate into the combinatorial CVD reactor
described above resulted in the extremely fast deposition (200 nmmin) of metal oxides at
temperatures as low as 130degC The films were characterized by ellipsometry and
Rutherford backscattering spectrometry The compositional spreads of 5 ndash 54 of Hf in
the HfO2SiO2 system and 5-62 of Zr in the ZrO2SiO2 system were proposed to result
from chemistry occurring between the two precursors A survey of possible reactions
involved in the deposition was discussed
Gladfelter 教授在中正大學化學暨生物化學系發表演講
- 31 -
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
Professor Axel GGriesbeck 訪問報告
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1訪問經過
Griesbeck 教授目前為科隆大學有機化學所教授為國際知名之有機光化學專家
亦為許多專書之編輯透過邀請他於 3 月 28 日上午抵台訪問停留台灣期間
赴中央研究院化學所淡江大學化學系台灣大學化學系訪問並作演講
2演講行程及概要
其訪問行程如下 328 (星期二) 清晨抵達台灣下午參觀故宮博物院 329 (星期三) 拜訪淡江大學化學系並發表演講與討論 330 (星期四) 拜訪中研院化學所並發表演講與討論 331 (星期五) 拜訪台灣大學化學系並發表演講與討論 41 (星期六) 前往花蓮太魯閣觀光 42 (星期日) 參觀台北 101 大樓午餐後離開台灣
3重要收獲及心得
Griesbeck 教授在台演講內容主要是有關有機光化學與光物理方面的研究是藉著
光誘導至分子的電子激發狀態來進行反應屬於綠色化學的一種他的研究特別
著重於產物之立體化學選擇性其乃透過激發態的電子自旋組態的控制與分子間氫
鍵的運用來達成他在中央研究院化學研究所演講題目為 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions於淡江大學化學系演講題目為 Photochemistry of amino acid derivatives stereoselective synthesis of beta-lactames and cyclobutanols於淡江大學化學系演講題
目為 New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity附件為其演講內容之摘要從其演講所帶來熱烈之討
論來看是一段成功的學術交流
4其他意見
Griesbeck 教授對於近年來很少有台灣學生申請德國宏博獎學金(Humbodlt fellowship)去德國從事研究感到不解與可惜訪問期間不斷地向接觸到的學生提供建
議並鼓勵申請也多次表示此次來訪對台灣的研究表現印象深刻他的親和力也利於國內
學者與其建立個人與學術關係
- 32 -
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
Attachment The abstract of Prof Axel Georg GRIESBECKrsquos talk Title 1 Spin-Selectivity in Photochemistry SingletTriplet Controlled Reactions involving Biradicals and Radical Ions Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state although both singlet and triplet state produce the cycloadducts with comparable chemoselectivity The correlation between selectivity and spin state was evaluated by concentration temperature and solvent viscosity studies The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-14-diyls for intersystem crossing (ISC) to the singlet manifold controlled preferentially by spin-orbit coupling This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity The role of hyperfine coupling is demonstrated by magnetic isotope effects
O
OPh
H
O
O
Ph [1] Griesbeck A G Abe M Bondock S Acc Chem Res 2004 37 919
Title II New Aspects of Type II Photooxygenation Polymer matrices antimalarial peroxides enantioselectivity
Preparative photooxygenation reactions using singlet excited molecular oxygen (1∆g-1O2 Type II reaction) is the prime example of green chemistry (air amp sunlight and some green leaves) What makes singlet oxygen capricious however is its constant refusal to fit into classical concepts of regio- and stereochemical control Furthermore the highest and thus synthetically most appealing lifetimes of singlet oxygen are reached in the gas phase (inexpedient) or in fluorinatedchlorinated solvents (not green) rarr In order to avoid these solvents (and solvents all) we have developed an effective yet simple approach for the singlet oxygen ene- and [4+2]-cycloaddition with organic substrates performed in tetraarylporphyrin-loaded or protoporphyrin IX-copolymerized polystyrene (PS) beads (see SEM-picture)12 Alternative solid supports investigated were cellulose acetate films PLA (polylactic acid) films PHB (polyhydroxy butyrate)
- 33 -
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
PEG (polyethylene glycol) films and PVAA (poly-N-vinylacetamid) polymer films The photooxygenation of the allylic alcohol mesitylol in different supports was used to map the polarity and the hydrogen-bonding network in the microenvironment rarr This photooxygenation approach was used for the synthesis of highly active antimalarial peroxides of the 124-trioxane type Boron trifluoride catalyzed peroxyacetalization opens the route to a broad diversity of monocyclic bicyclic and spirobicyclic peroxides with antimalarial and anti-tuberculosis activity (see the adamantylidene compound)3
1 A G Griesbeck T El-Idreesy A Bartoschek Pure Applied Chem 2005 77 1059 2 A G Griesbeck T El-Idreesy A Bartoschek Adv Synthesis amp Catalysis 2004 346 245-251 3 A G Griesbeck T El-Idreesy O Houmlinck J Lex R Brun Bioorg Med Chem Lett 2005 15 595 Title 3 Photochemistry of amino acid derivatives stereoselective synthesis of β-lactames and cyclobutanols In recent years we have explored the photochemistry of NO-activated α-amino acids Three major processes were observed following electronic excitation γ- and δ-hydrogen abstraction and electron transfer The synthesis of isodehydrovalin from valin is an example of efficient sequential γ-δ-hydrogen transfer Yang-type cyclizations were obtained from pyruvamides and propiophenone derivatives of aliphatic amino acids1
Surprisingly high lifetimes were determined for the triplet 14-biradicals generated from γ-branched α-hydroxy as well as α-acyloxypropiophenones in contrast to the α-amido-substituted analogs with τ lt 200 nsec these biradical live 3-4 microsec in benzene solution2[1] A G Griesbeck H Heckroth J Am Chem Soc 2002 124 396 [2] X Cai P Cygon B Goldfuss A G Griesbeck H Heckroth M Fujitsuka T Majima Chemistry Eur J 2006 in print
OHO H N h
N H2N
COOMe COOMeO COOH
O
O HOPh
ON H
COOMe
Ph
N H
COOMe
O
AcHN COAr
Me NHAc OH
Ar
H
HH
h
h szlig-lactams
HOHMe
h OHHO
HArCOAr H
cyclobutanols
- 34 -
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
WESTFAumlLISCHE WILHELMS-UNIVERSITAumlT
MUumlNSTER
Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149 Muumlnster Institut fuumlr Physikalische Chemie Prof Dr Hellmut Eckert D-48149 Muumlnster 25 July 2006 Corrensstrasse 30 Telefon (0251) 83-29161 Telefax (0251) 83-29159 E-mail ECKERTHuni-muensterde
- 35 -
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
Dr Jerry C C Chan Department of Chemistry National Taiwan University Taipei Report on the visit at National Taiwan University February 23-27 2006
I very much appreciated the opportunity of spending five inspiring days visiting three
different Chemistry departments at the invitation of the National Taiwan University
Following my arrival on Feb 23 I visited Academia Sinica in the afternoon I had several
interesting discussions with the colleagues M Tzou T Lin C T Chen and LS Kan who
gave me an overview of their current research activities In my research seminar on the
topic ldquoSite Connectivities and Cation Distributions in Ion Conducting Glassesrdquo I
described and illustrated the use of advanced solid state nuclear magnetic resonance
methodology for the structural analysis of medium-range order processes in various ion
conducting glass systems Using such techniques it was possible to provide new insights
into the spatial distributions of mobile ions (such as lithium and sodium) in various
different network glasses As one particular result we could demonstrate that the cations in
alkali silicate glasses tend to be heavily clustered whereas in most of the other oxide glass
systems (borate phosphate tellurite germanate glasses) the ions are arranged in a mostly
statistical fashion This particular difference also manifests itself in the way the electrical
conductivities and activation energies depend on glass composition
February 24th was spent at National Taiwan University During the morning several
students of the JCC Chan group (the group hosting me at NTU) made oral presentations
which related to their current PhD or Masters projects and which were discussed in the
group afterwards Subsequently I had the opportunity to meet several faculty members (JT
Cheng S Cheng S H Chiu S T Liu C Y Moe and TY Luh) to learn about their work
and explore possibilities for collaboration I was very impressed by the activities on
supramolecular chemistry as well as on inorganic-organic hybrid and nanostructured
materials championed by this department and there are many common interests In the
afternoon I presented my research seminar on the preparation and characterization of
various ternary alumina-based sol-gel derived glasses Using aluminium lactate as a novel
precursor it has been possible to extend the glass-forming ranges of the systems
Na2O-Al2O3-P2O5 and Na2O-Al2O3-B2O3 and Al2O3-B2O3-P2O5 significantly As outlined
in my talk single- and double resonance solid state NMR methodology has proven very
- 36 -
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
powerful for developing structural concepts for these materials
Apart from my research talk I took the opportunity to introduce the audience to a new PhD
program initiated at the University of Muenster called the ldquoInternational Graduate School
of Chemistryrdquo (GSC) Within this programme for which I am currently serving as Chair
16-18 three-year fellowships are awarded each year to qualified applicants from all over
the world Suitable candidates are selected for personal interviews on the basis of their
academic performance during Undergraduate and Masters studies and each year about 50
candidates are invited for interviews Fellowships awarded (about euro1300) include tuition
and fees as well as personal salaries In addition support is available for research
equipment supplies research-related travel and cultural exchange The programme
features an interdisciplinary curriculum with all the courses fully taught in English
language and the progress of each student is supervised by a committee consisting of three
faculty members At present about 100 students from 23 nations have participated in the
GSC but to the date we have had no students from Taiwan yet and hope to be able to
change this as fast as possible We warmly invite current Master students from NTU to
apply to our program For the new academic year (which starts in October 2006) the
application deadline is April 30 2006 Overall my proposal to consider qualified NTU
Graduates for admission to this programme met with lots of interest from students faculty
members and administration officials
Saturday February 25th was spent in the laboratories of the JCC Chan group About
30-60 minutes were spent on discussing each of the studentsrsquo projects The work on the
characterization of biologically active ceramics and on the interaction of biomolecules with
fluoroapatite surfaces was of special interest to me because we are pursuing similar
activities in our institute I was very impressed by the results the group shared with me
leading me to conclude that the Chan group is making excellent progress in becoming one
of the major players in this research area I was also able to make some specific
suggestions for some complementary NMR experiments which are suitable to enhance this
research agenda Furthermore I took the opportunity of interviewing one of Jerryrsquos
undergraduate research students who had applied for a three-month Undergraduate
research fellowship (sponsored by the Graduate School of Chemistry) in my laboratory I
was very impressed by his knowledge research experience (he is working on the synthesis
and characterization sol-gel derived boron silicates a research area also of interest for us)
and by his dedication to research He will be offered this fellowship and we are hoping to
be able to attract him to our department and the Graduate School of Chemistry
- 37 -
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
Sunday February 26th was spent for re-creation Three students from the JCC Chan
group picked me up and showed me the tallest building in the world This excursion gave
us another nice opportunity to continue some of our scientific discussions from the day
before
On Monday February 27th I visited the Chemistry department of National Tsing Hua
University A major research agenda of this school is conducting cutting-edge research in
the area of mesoporous materials and I enjoyed the discussions with Dr CM Yang (my
host) and his colleagues Drs S L Wang and K J Chao very much Several groups have a
distinguished research record in solid state NMR which can be put to good use for the
characterization of the catalytic materials developed by various groups in this department
For a research seminar I decided to give the same talk I had given at Academica Sinica
Again my proposal of considering some applications from Tsing Hua University for our
Graduate School of Chemistry met with much interest with the students scientific
colleagues as well as the departmental chairman
My visits to Academica Sinica National Taiwan University and National Tsing Hua
University were not only inspiring from the point of view of discussing joint research
interests but also by broadening my knowledge on the Taiwanese educational and
academic system I am confident my visit has been useful for helping to increase future
interactions with German universities and with the Westfaumllische Wilhelms-Universitaumlt
Muumlnster in particular With regard to training some PhD students from Taiwan within the
frame of the GSC-MS and exploring further avenues of such international cooperation in
research and graduate education I will remain in touch with my hosts Drs JCC Chan
(NTU) and Dr CM Yang (THU)
Again many thanks for giving me the opportunity for this inspiring visit
With best regards
Professor Hellmut Eckert
Institute of Physical Chemistrry
Westfaumllische-Wilhelms-Universtitaumlt Muumlnster
- 38 -
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
訪問教授訪問報告表
姓名Jan-Erling Baumlckvall 教授
訪問日期民國 95 年 3 月 19 日 至 民國 95 年 3 月 25 日
接待機構台大化學系 接待人 陸天堯教授 聯絡電話02-33664088
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
95319 抵台
95320 師大化學系
95321 中研院化學所
95322 中研院化學所
95323 台大化學系
95324 台大化學系
95325 離台
2 演講行程及概要
Jan-Erling Baumlckvall 教授於 319 抵台320 於師大化學系以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講321 於中研院化學所同樣以「Transition Metal Catalysis in Biomimetic Oxidations」為主題作專題演講並與多位研究員﹝呂光烈研究員簡淑華研究員劉行讓研究員羅芬台研究員李文山研究員劉陵崗研究員﹞進行學術研究交流323 於台大化學系以「Recent Advances in Combination of Metal and Enzyme Catalysis for Asymmetric Synthesis」為題發表演說並與陸天堯教授梁文傑教授汪根欉教授劉緒宗叫受陳竹亭教授方俊民教授楊吉水教授邱勝賢教授訪談進行學術交流並洽談學術合作事宜
3 重要收獲及心得
Jan-Erling Baumlckvall 教授任職於瑞典斯德哥爾摩大學其專長領域是有機化學Jan-Erling Baumlckvall 教授是結合有機金屬化學及酵素催化反應的先驅者是此領域的權威研究者此研究領域在學術上及工業上都有廣泛的應用
台灣大學與瑞典斯德哥爾摩大學是締約學校雙方有交換學生計畫Jan-Erling Baumlckvall 教授此次來台訪問化學系與其討論進ㄧ步的學術交流合作希望能透過教授的互訪學生的交換雙邊研討會的舉辦研究計畫的合作等方式加強雙方的了解及促進雙方深ㄧ步的合作
4其他意見
無
- 39 -
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
訪問教授訪問報告表
姓名Andrie Ayral
訪問日期民國 95 年 5 月 13 日 至 民國 95 年 5 月 19 日
接待機構清華大學化學系 接待人 趙桂蓉 聯絡電話03-5720964
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Montpellier 大學教授及歐洲薄膜中心資深研究員 Professor Andrie Ayral 此行應化
學中心之邀抵台訪問停留期間除了在東華大學化學系中原大學薄膜中心
清華大學化學系作了三場演講及討論外並赴國家同步幅射中心討論
2 演講行程及概要
Ayral 教授於 5 月 13 日傍晚抵達台灣第二天(星期日)遊覽了台灣大學故宮等台北重要景點5 月 15 日 一早赴花蓮在東華大學作一場演講題目
為rdquoInnovative optical methods for the characterization of porous thin filmsrdquo並與該校
老師及訪問該校的的台大化學系王瑜教授討論第二天稍作參訪後返抵新竹5月 17 日一早訪問清華大學及同步幅射中心下午在清華化學系作演講題目
為rdquoDesign strategies for ceramic membranesrdquo 第二天早上繼續學術討論中午赴
中壢中原大學薄膜中心(組員以化工教授為主包括台大中原中央元智等) 於中心作演講題目為rdquo Silica-based membranes use opportunities and limitationsrdquo演講後參觀該中心(此中心為國內唯一的薄膜中心與法國歐洲薄膜中心作有機
薄膜的成員有合作關係彼此曾召開雙邊會議)5 月 19 日討論及遊覽新竹下
午教授回法國
3 重要收獲及心得
每場演講內容豐富目前無機薄膜的發展及應用在國際上被重視及看好Ayral 教授在的歐洲薄膜中心為歐洲薄膜研究的重鎮以之為中心與十幾個分散在英
國德國西班牙比利時葡萄牙等的據點形成一個研發網互相交流Ayral教授的來訪及演講拓寬了我們在無機薄膜上的知識及瞭解同時他希望近期與我
們達成合作關係此點是相當重要的收穫
4其他意見
Ayral 教授態度認真而誠懇最近幾年常為國際無機薄膜或材料會議邀請主題演講今
年暑期還主辦此屆的國際無機薄膜會議此次來訪討論如何設計有應用潛力的材料及
用基本科學研究的精神去思考及方法去作分析作了很好解說及示範學生因陪伴他在
台北及赴花蓮遊覽也見識到不少他很客氣及禮貌對研究生是一個好的榜樣
- 40 -
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
訪問教授訪問報告表
姓名Prof Charles Riordan
訪問日期民國 95 年 5 月 18 日 至 民國 95 年 5 月 25 日
接待機構清華大學化學系 接待人 廖文峯教授 聯絡電話03-5715131ext 35663
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
Prof Riordan 於 5 月 19 日訪問台大化學系演講題目為Dioxygen Activation at Monovalent Nickel 5 月 22 日訪問中研院化研所於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents由呂光烈
教授負責安排演講事宜5 月 23 日訪問嘉義大學於化研所有一場演講題目為
Organonickel Intermediates in Biocatalysis Synthesis and Chemical Precedents於 5 月 24日訪問清華大學化學系除與系上教授交換研究心得之外於系上之演講題目為
Dioxygen Activation at Monovalent Nickel5 月 1920 日 Prof Riordan 參觀故宮博物館
及美術館5 月 25 日上午離台返回 Delaware
2 演講行程及概要
Prof Riordan 於 5 月 19 日訪問台大化學系演講 5 月 22 日訪問中研院化研所5 月
23 日訪問中研院化研所於 5 月 24 日訪問清華大學化學系
3 重要收獲及心得
Prof Riordan 係 Univ of Delaware 之教授主要研究興趣在無機生化方面於來訪
期間與國內無機生化教授們有相當深入之討論有關無機生化之未來走向及有關無
機生化目前所關切的問題如金屬酶化學金屬在生物結構中的角色金屬在基因
蛋白體的化學作用hellip等等有相當深入的討論
4其他意見
- 41 -
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
-
訪問教授訪問報告表
姓名 Johannes G Vos
訪問日期民國 95 年 6 月 2 日 至 民國 95 年 6 月 10 日
接待機構 清華大學化學系 接待人 季昀 教授 聯絡電話 03 5712956
訪問重要成果 (如篇幅不足另以A4 白紙填寫)
1 訪問經過
于六月二日晚間抵達十日晚間離台在台灣停留共八個晚上訪問四個學術
研究單位其餘的時間則用以參觀台北新竹近郊的風景名勝景點
2 演講行程及概要
六月五日訪問淡江化學系六月七日訪問清華化學系六月八日訪問中研院化
學所六月九日訪問台大化學系演講摘要如下
Ruthenium Polypyridyl Chemistry from basic research to application and back again
Since the late 1970rsquos interest in the chemistry and applications of Ruthenium polypyridyl complexes has increased steadily In this presentation the development of this area is tracked and discussed taking into account new scientific developments as well as novel applications This overview will be based on work carried out in our laboratories over the last 25 years on ruthenium and osmium polypyridyl compounds Issues addressed will be synthetic chemistry polymer films and monolayers electrochemical and luminescent sensors supramolecular chemistry photophysics and electrochemistry of dinuclear compounds The interaction between basic and applied research is of particular interest and selected examples are highlighted
3 重要收獲及心得
能夠更進一步瞭解未來無機化學的研究方向為最重大的收穫
4 其他意見
該訪問教授將於 2007 年在 Trinity College Dublin Ireland 主辦一場研討會
主題為
17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds Towards a Brighter Future with Photonic Materials Photoelectronics Nanotechnology Biodiagnostics and Solar Energy 研討方向與國內未來研究趨勢契合應值得參加
- 42 -
- Attachment The abstract of Prof Wayne L Gladfelterrsquos talk
- Attachment The abstract of Prof Axel Georg GRIESBECKrsquos tal
- Institut fuumlr Physikalische Chemie Schloszligplatz 47 D-48149
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