Polymer Matrials Lab.
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Hyperbranched polymer Lipid and Protein 고고고고고고고 고고고고고 / 고고고고고고고고 / 고고 2 고 고 고 고 1999. 12. 9 Content s Hyperbranched polymer Introducton definiton of terms dendrimer 고 hyperbranched polymer 고 고고 history and advantage General polymerization with ABx mono mer New approach with A 2 and B 3 monomer Lipid Introduction Cross-linking polymerization Polymerized liposome Protein Nylon Surface modification with protein
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Polymer Matrials Lab. 고분자신합성법. Hyperbranched polymer Lipid and Protein. 공업화학과 / 고분자재료연구실 / 석사 2 기 윤 경 준. Contents. Hyperbranched polymer Introducton definiton of terms dendrimer 와 hyperbranched polymer 의 비교 history and advantage General polymerization with ABx monomer - PowerPoint PPT Presentation
Transcript of Polymer Matrials Lab.
Hyperbranched polymerLipid and Protein
고분자신합성법
공업화학과 / 고분자재료연구실 / 석사 2 기
윤 경 준
1999. 12. 9
ContentsHyperbranched polymer
Introducton definiton of terms dendrimer 와 hyperbranched polymer 의 비교 history and advantage
General polymerization with ABx monomer
New approach with A2 and B3 monomer
LipidIntroductionCross-linking polymerization Polymerized liposome
ProteinNylonSurface modification with protein
Hyperbranched Polymer
Definition of termsDendritic polymer, cascade polymer, starburst polymer, arborol A highly branched polymer of precisely controlled branching structure produced by a sequence of step-growth polymerization reaction steps. – reference : Polymer Science Dictionary, Synthesis of polymer Dendrimer 와 Hyperbranched Polymer 의 비교Dendrimer : 분자량 분포가 monodisperse 하고 구형에 가까우며 최외각에 많은 작용기를 갖 는다 . 합성에는 연속적인 반응과 정제과정이 수반되는 어려움이 있다 . Hyperbranched Polymer : 분자량 분포가 monodisperse 하지는 않지만 globular 구조를 가지 며 외각에 많은 작용기들이 존재한다 . ABx 형태의 단량체를 간편하게 “ one-pot” 중합 하여 제조 가능하다 .
The intrinsic viscosity [] of polymers related to their molecular weight.
Hyperbranched polymers
dendrimers
Linear polymers
Log
[]
Log M
History1952 년 Flory 의 예측ABx 형 단량체 중합 – 작용기 A : 1 개 , 작용기 B : n(x-1)+1 개 (n= 중합도 )낮은 물성으로 인하여 주목 받지 못함 .
AdvantageHyperbranched polymers might be a good alternative to dendrimers, as they can be produced on a large scale at a reasonable cost.
Hyperbranched Aliphatic PolyestersA. Hult, Macromolecules 1995, 28, 1698-1703
ObjectsNew hyperbranched polymer Large scale production
Reaction scheme
Degree of Branching – 13C NMR
DB =dendritic units + terminal units
dendritic units + terminal units + linear units
For ideal dendritic substance, DB = 1
Possible repeating units in the hyperbranched polyesters
Chemical shift for model compounds in acetone-d6
For theoritical generation 7 DB = 83%
Synthesis of Hyperbranched Aromatic polyamid from Aromatic Diamines and Trimesic Acid – New approachMacromolecules 1999, 32, 2061-2064
General methodABx monomer : not commercially available monomer 합성에 장시간 소요New methodA2 : commercially available for linear + condensation polymerB3 :available as branching or cross linking agent
Polymerization A2 and B3 in most caseBranching, cross-linking, cyclization (insoluble in any organic solvents)
Consideration of reaction condition Hyperbranched polymer from A2 and B3
2 : 3 = feed ratio
Reaction condition : polymerzation at 80C for 3 h with the total monomer concentration of 0.21mol/L(3.3 wt%) in 80ml solvent (NMP) no gelation, soluble in organic solvent in 50ml solvent gelation, insoluble in organic solvent
Introduction
• Self-assembly : A process in which a Complex hierarchical structure is established without external intervention.
: 비극성 유기용매의 추출에 의해 세포나 조직으로부터 분리되는 자연계에 존재하는 유기분자종류 : 지방 , 왁스 콜레스테롤 , 스테로이드Self assembling lipid soap : 긴사슬 지방산의 sodium 혹은 potassium 염의 혼합물 phospholipid : phophoglyceride, sphingolipid
Lipid
Cross-Linking Polymerization in Two-Dimensional AssembliesMacromolecules 1999, 32, 5519-5524Macromolecues 1996, 29, 8321-8329
Introductionmonomeric amphiphilic lipid -------polymerization ---- linear polymer or corss-linked polymer
Depending on the number and location of polymerizable groups per monomer
Liposome 화
Various monomeric amphiphilic lipid
polymerizationThermal AIBN polymerization
Redox polymerizaton with K2S2O8 and NaHSO3
Diret photoirradiation
Result
Stability of polymeric lipidsCross-linked lipid more stable with surfactant
Emulsion – 액체 중에 그 액체와 혼합되지 않는 다른 액체의 미립자를 유화제의 도움을 받아 안정하게 분산시킨 것Liposome – 인지질을 물에 현탁시킨 2 분자막의 폐쇄 소포Advantage – high biocompatibility Drawback – stabilityApplication – drug delivery, biosensor etc.
Polymerized liposomeLangmuir 1998, 14, 1974-1976
IntroductionAdvantage : physical stability, durability during chemical modification
SystemDiacetylen functionalized lipid ------Form conjugated system (blue)--------
Perturbation of orbital overlap (red color)
Uv light
Binding Virus,toxin
: -amino acid residue
가 아미드결합된 거대 생체분자
protein
단백질의 구조• Primary structure : 아미노산 잔기의 결합서열• Secondary structure driving force : hydrogen bond 약 5kcal/mol• Tertiary sturcture driving force : 탄화수소 곁사슬의 소수성 상호작용 cyteine 잔기사이에 이황화물 다리의 형성 , hydrogen bond, salt bridge 등
피브로인의 병풍구조
케라틴의 나선형 구조
미오글로블린의 2 차및 3 차구조
Aminoic acid
Nylon – polyamide, interchain hydrogen bondingMacromolecules 1998, 31, 8540-8548
Polymerization• diacid + diamine• amino acid• ring opening of lactam
structure
Surface modification with protein
(a) odd (b) even number of methylenes in the diamine unit
Langmuir 1997, 13, 6485-6490
Advantage : improve wettability and biocompatiblity
Method Physical : hydrophobic or electrostatic interaction reversible buffer, detergent, other protein
Chemical : covalent bonding irreversible, more popular
