37th International Symposium on Capillary Chromatography · Poster Information Poster Sessions Each...
Transcript of 37th International Symposium on Capillary Chromatography · Poster Information Poster Sessions Each...
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37th International Symposium
on Capillary Chromatography Frantisek Svec, Lawrence Berkeley
National Laboratory
Robert E. Synovec, University of Washington
10th GC×GC Symposium Jean-Marie Dimandja, Spelman College
Philip Marriott, Monash University
May 12-16, 2013
Renaissance Palm Springs
Palm Springs, CA USA
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Table of Contents
Acknowledgements ............................................................................................
Program Partners and Exhibitors ......................................................................
Media Partners ..................................................................................................
General Information ..........................................................................................
Social Program ..................................................................................................
Poster Information ............................................................................................
Proceedings .......................................................................................................
Travel Award Recipients and Best Poster Awards ...........................................
Schedule-At-A-Glance GC×GC ........................................................................
Scientific Program Summary – GC×GC Oral Program ....................................
Scientific Program Summary – GC×GC Posters ...............................................
Schedule-At-A-Glance ISCC .............................................................................
Scientific Program Summary – ISCC Oral Program .........................................
Scientific Program Summary – ISCC Posters ...................................................
Scientific Program Summary – Technical Seminars .........................................
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Acknowledgements
GC×GC Co-Chairs:
Jean-Marie Dimandja (USA)
Philip Marriott (Australia)
GC×GC Scientific Committee:
Jean-Marie Dimandja (USA)
Hans-Gerd Janssen (The Netherlands)
Philip Marriott (Australia)
Luigi Mondello (Italy)
John Seeley (USA)
Robert E. Synovec (USA)
ISCC Co-chairs:
Frantisek Svec (USA)
Robert E. Synovec (USA)
ISCC Scientific Committee:
Francesco Dondi (Italy)
Hans-Gerd Janssen (The Netherlands)
Kiyokatsu Jinno (Japan)
James Jorgenson (USA)
Robert Kennedy (USA)
Milton Lee (USA)
Luigi Mondello (Italy)
Milos V. Novotny (USA)
J. Michael Ramsey (USA)
Pat Sandra (Belgium)
ISCC Organizing Committee:
John Hinshaw (USA)
Ronald E. Majors (USA)
Joseph J. Pesek (USA)
Robert L. Stevenson (USA)
Joshua Whiting (USA)
Audio-Visual: Michael Johnstone, MJ Film/Video Productions
Symposium Management at CASSS Stephanie L. Flores, CAE, CASSS Executive Director
Renee Olson, Symposium Manager
Catherine Stewart, Finance Manager
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The Organizing Committee gratefully acknowledges the corporate partners for their
generous support of academia:
Diamond Program Partner
Thermo Scientific
Platinum Program Partners
Restek Corporation
Shimadzu Scientific Instruments, Inc.
Gold Program Partner
ALMSCO International
Silver Program Partner
Elsevier
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Exhibitors
Agilent Technologies
ALMSCO International
Elsevier
Entech Instruments, Inc.
ISCC and GC×GC 2014
Peak Scientific
Polymicro Technologies, a Subsidiary of Molex
LECO Corporation
Restek Corporation
Shimadzu Scientific Instruments, Inc.
Supelco, A Member of the SIGMA-ALDRICH
Group
Thermo Scientific
Zoex Corporation
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Leading Media Partner
Technology Networks
Media Partners
LCGC North America
Springer Verlag
The Analytical Scientist
Wiley-VCH Verlag GmbH & Co. KGaA
Supporting Organization
Gulf Coast Conference
Travel Grant and Award Supporters
BP
CASSS, an International Separation Science
Society
Chromaleont
LECO Corporation
PerkinElmer
Restek Corporation
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General Information
Venue Renaissance Palm Springs Hotel
888 Tahquitz Canyon Way
Palm Springs, California 92262
Phone: (760) 322-6000
Name Badges Please wear your name badges in order to gain admittance to the meetings, poster
sessions, exhibit hall and social functions.
Registration Short Course and Workshop Registration will be available Sunday, May 12 from 8:30 am
– 3:00 pm in the Ballroom Foyer.
Registration for the Conference will be located in the Ballroom Foyer. Registration will
be available Sunday, May 12 starting at 2:00 pm through Thursday, May 16 at 4:30 pm.
Photographic Equipment The use of cameras is NOT permitted during the lecture program, workshops or poster
sessions. Cameras are permitted on the exhibit floor. However, permission from the
vendors involved must be obtained before photographs can be taken.
Job Postings
Boards will be available in the Pasadena, Sierra and Ventura Ballrooms to post positions
available or wanted. This will be available all week.
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Social Program
Sunday – 18:00 – 19:00 – GC×GC 10th
Anniversary Celebration
Renaissance Palm Springs – Ballroom Courtyard
GC×GC attendees come join us as we celebrate the 10th
Anniversary of the GC×GC
Symposium.
Monday – 19:00 – 21:00– Special Event
Renaissance Palm Springs – Pool Deck
Enjoy the sun and old Hollywood flair of Palm Springs. This is a great opportunity to
mingle with colleagues while you enjoy a few drinks and some food on us.
Entertainment includes a visit from old Hollywood and fun activities to make memories
at this year’s conference. Please make sure you have your badge as it is your ticket to the
event. Dress is casual.
Tuesday – 17:30 – 19:00 – Exhibitor Reception
Renaissance Palm Springs – Ballroom Foyer
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Poster Information
Poster Sessions
Each poster board measures 4 ft. high by 8 ft. wide. Pushpins will be available in
the exhibit hall.
All posters will be set up the entire four days of the Symposium in the Pasadena,
Sierra and Ventura Ballrooms.
Poster boards are labeled with the number corresponding to the abstract number
shown in the program.
Posters can be viewed during breakfast, breaks and poster sessions on…
o Monday, May 13 14:00 – 15:30
o Tuesday, May 14 14:00 – 15:30
o Wednesday, May 15 14:00 – 15:30
Authors must be in attendance at their posters during the hours listed in the
program.
All materials must be removed between 3:30 - 4:00 pm on Wednesday, May 15, 2013
or they will be discarded. When taking down your poster, please also remove the
pushpins from your own board. Also, remember to take any business cards that are in
your envelope – these people are requesting reprints of your abstract.
Key to Poster Board & Abstract
First Symbol = P = Poster
Second Symbol = Poster Number
Third Symbol = Day
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Proceedings for Conference
Participants are cordially invited to submit a full-length manuscript for publication in a
regular issue of the JOURNAL OF CHROMATOGRAPHY A that will be followed by a
virtual special issue devoted specifically to the ISCC and GC×GC Symposium. This is a
totally new concept which essentially rules out possible delays in publication for
contributors to the special issue and hopefully – with the options for videos and
additional (colour) photos which would not be included in a printed issue – will make this
special conference issue more complete and accessible than it has ever been.
This approach has the following advantages:
Papers are published individually in regular issues as soon as they are accepted.
Footnotes indicate at which conference they were presented, and are the source
for selection and linking to the virtual special issue.
The virtual special issue is prepared and placed on the Journal of Chromatography
A special issue site – with links to papers in Science Direct.
Preface and possible photos – with the added possibility of presenting videos e.g.
from poster sessions, will also be available via the virtual special issue that is an
expanded special issue available only online
Points to note:
When preparing your manuscript please follow carefully the Guide to Authors,
which you can find on the online submission site http://ees.elsevier.com/chroma.
Submit your manuscript via the journal’s online submission and reviewing system
at http://ees.elsevier.com/chroma. This expedites the review and acceptance
process.
In your cover letter please mention that your manuscript is intended for the
special online issue covering the ISCC/GC×GC symposium.
All manuscripts will be subject to the usual selection process including the strict
peer review procedure. The acceptance for presentation at the meeting does not
guarantee publication in the journal.
A separate dedicated video website can also contain videos comprised of a
PowerPoint presentation or graphics presented along with an audio commentary
given by you, the presenter, or one of your colleagues. This is intended to be
added as part of the “expanded” virtual issue, and will not be included in the
regular issues of the journal. If you wish to submit your poster presentation,
please contact the journal for a template and further instructions.
Elsevier will send detailed submission instructions to individual participants before and
after the conference.
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Travel Award Recipients
CASSS and Chromaleont Travel Grants
Will Black, University of North Carolina, Chapel Hill, NC USA
Sung-Tong Chin, Monash University, Clayton Australia
James Grinias, University of North Carolina, Chapel Hill, NC USA
Dulan Gunasekara, University of Kansas, Lawrence, KS USA
Darina Kačeriaková, Institute of Analytical Chemistry, Bratislava, Slovakia
Anastasiia Kanatyeva, Institute of Petrochemical Sinthesys, RAS, Moscow, Russia
Alexandros Lamprou, Lawrence Berkeley National Laboratory, Berkeley, CA USA
Richard Lidster, University of York, York, United Kingdom
Fernando Maya Alejandro, Universitat de les Illes Balears, Palma De Mallorca, Spain
Kari Organtini, Penn State University, University Park, PA USA
Pierre-Hugues Stefanuto, University of Liège, Liège, Belgium
Best Poster Awards
Richard Sacks GC×GC Poster Award
The Richard Sacks awards will be presented for the first time at closing of the 2013
GC×GC Symposium, and have been instituted to honor the late Prof. Richard D. Sacks
(1943-2006). Prof. Sacks was an internationally recognized scientist for his work on
analytical instrumentation in atomic emission spectroscopy and gas chromatography (GC
inlet systems, high-speed GC, miniature GC and GC×GC). Prof. Sacks was also an
outstanding teacher at the University of Michigan for 37 years, and a strong supporter of
young undergraduate and graduate school researchers throughout his career. These
awards will be given to the top 3 student posters presented at the GC×GC conference.
This year the awards are sponsored by BP.
ISCC Poster Award
Posters presented at ISCC 2011 are reviewed by an international panel of scientists.
Posters will be up all week. Winners of the poster awards for ISCC will be announced
during the plenary session on Thursday, May 16.
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GC×GC 2013
Scientific Program Summary
Sunday, May 12, 2013
07:30 – 14:00 Registration GC×GC Short Course ONLY in the Ballroom Foyer
08:30 – 15:30 GC×GC Short Course in the Andreas Room
14:00 – 17:00 Registration in the Ballroom Foyer
18:00 – 19:00 10th
Anniversary GC×GC Celebration at the Ballroom
Courtyard
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Monday, May 13, 2013
07:30 – 18:30 Registration in the Ballroom Foyer
Plenary Lecture in the Catalina and Madera Ballrooms Session Chairs: Jean-Marie Dimandja, Spelman College, Atlanta, GA USA
and Philip Marriott, Monash University, Clayton, Australia
08:30 – 08:45 GC×GC Introduction, Welcome and Presentation of the
GC×GC Scientific Achievement Award
Jean-Marie Dimandja, Spelman College, Atlanta, GA USA
Philip Marriott, Monash University, Clayton, Australia
08:45 – 09:15 (L-01-01)
GC×GC: In Hot Pursuit of More Chemical Information Robert E. Synovec, University of Washington, Seattle, WA USA
09:15 – 9:30 Mini Break
Instrument Development in the Catalina and Madera Ballrooms Session Chairs: Jean-Marie Dimandja, Spelman College, Atlanta, GA USA
and Philip Marriott, Monash University, Clayton, Australia
09:30 – 09:55 (L-01-02)
Using a Simple Selectivity Model to Design Better GC×GC
Separations John Seeley
1; Abhijit Ghosh
1; Stacy Seeley
2,
1Oakland University,
Rochester, MI USA; 2Kettering University, Flint, MI USA
09:55 – 10:20 (L-01-03)
Separation and Identification of 'Supercomplex' Mixtures of
Toxic Organic acids by GC×GC-High Resolution-MS with
Ionic Liquids: a 'Hump' No More!
Steven Rowland, Plymouth University, Plymouth, United Kingdom
10:20 – 10:40 (L-01-04)
GC×2GC and 2GC×GC using Contra-Directional Thermal
Modulation Benjamin Savareear
1; Laura Tedone
2; Robert Shellie
1;
1ACROSS,
University of Tasmania, Hobart Australia; 2University of Messina,
Messina Italy
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Monday, May 13, 2013 continued…
10:40 – 11:00 (L-01-05)
Hybrid Comprehensive Two-Dimensional – Multidimensional
Gas Chromatography (GC×GC-MDGC): Potential and
Applications Blagoj Mitrevski; Leesun Kim; Philip Marriott, Monash
University, Clayton, Australia
11:00 – 11:30 AM Break – Visit the Exhibitors and Posters in the Foyer and
Pasadena, Sierra and Ventura Ballroom
Optimization in GC×GC in the Catalina and Madera Ballrooms Session Chairs: Chiara Cordero, University of Turino, Turino, Italy
and John Seeley, Oakland University, Rochester, MI USA
11:30 – 11:55 (L-01-06)
Optimization Aspects in Comprehensive Two-Dimensional Gas
Chromatography
Tadeusz Gorecki; Ahmed Mostafa; Matthew Edwards, University
of Waterloo, Waterloo, ON Canada
11:55 – 12:20 (L-01-07)
Optimization of Column Formats and Flow Conditions in
GC×GC
Hans-Gerd Janssen1; Daniela Peroni
2;
1Unilever, Vlaardingen, The
Netherlands; 2University of Amsterdam, Amsterdam, The
Netherlands
12:20 – 12:40 (L-01-08)
Gas Velocity at the Point of Re-Injection: An Additional
Parameter in Comprehensive 2D GC Optimization
Peter Tranchida1; Luigi Mondello
1,2,
1SCIFAR, University of
Messina, Messina, Italy; 2C.I.R., Campus Bio-Medico, Rome, Italy
12:40 – 13:00 (L-01-09)
Use of Multidimensional Retention Normalization in Predictive
GC×GC for Column Set Selection and Separation
Optimization
Jean-Marie Dimandja, Spelman College, Atlanta, GA USA
13:00 – 14:00 Lunch Break – Participants on their own
14:00 – 15:30 Poster Session – Visit the Exhibitors and Posters in the Foyer and
Pasadena, Sierra and Ventura Ballroom
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Monday, May 13, 2013 continued…
GC×GC Applications I in the Catalina and Madera Ballrooms Session Chairs: Debora Almeida Azevedo, Federal University, Rio de Janeiro, Brazil
and Philip Marriott, Monash University, Clayton Australia
15:30 – 15:50 (L-01-10)
GC×GC: The Importance of Second Dimension Column
Length in Promoting True Peak Capacity Increase
Comprehensive Two-Dimensional Gas Chromatography Jack Cochran
1; Michelle Misselwitz
1, Julie Kowalski
1, Mark
Merrick2,
1Restek Corporation, Bellefonte, PA USA;
2LECO
Corporation, St. Joseph, MI USA
15:50 – 16:10 (L-01-11)
Application of Comprehensive Two-dimensional Gas
Chromatography to the Analysis of Volatile Compounds of
Brazilian Wines
Juliane Elisa Welke1; Vitor Manfroi
2; Mauro Zanus
3; Marcelo
Lazzarotto3; Claudia Alcaraz Zini
1,
1Instituto de Química;Porto
Alegre, Brazil 2Instituto de Ciência e Tecnologia de Alimentos,
Universidade Federal do Rio Grande do Sul, Porto Alegre, Brazil; 3Embrapa Uva e Vinho, Bento Gonçalves, Brazil
16:10 – 16:30 (L-01-12)
Evaluation of GC - Online Reduction × GC for the Separation
of Fatty Acid Methyl Esters Pierluigi Delmonte; Ali Reza Fardin Kia; Jeanne I. Rader, FDA,
College Park, MD USA
16:30 – 16:50 (L-01-13)
Extending the Orthogonality to the Whole Analytical Process:
Does it Open New Perspectives in Flavoromics? Chiara Cordero; Cecilia Cagliero; Erica Liberto; Luca Nicolotti;
Patrizia Rubiolo; Barbara Sgorbini; Carlo Bicchi, University of
Turino, Turino, Italy
16:50 – 17:20 PM Break – Visit the Exhibitors and Posters in the Foyer and
Pasadena, Sierra and Ventura Ballroom
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Monday, May 13, 2013 continued…
GC×GC Applications II in the Catalina and Madera Ballrooms Session Chairs: Blagoj Mitrevski, Monash University, Clayton, Australia
and Luigi Mondello, SCIFAR, University of Messina, Messina, Italy
17:20 – 17:40 (L-01-14)
TD-GC×GC-TOFMS Study of Human Cadaveric VOC
Profiles
Pierre-Hugues Stefanuto1; Sonja Stadler
2; Romain Pesesse
1; Kayte
Perrault3; Shari Forbe
3s; Jean-Francois Focant
1,
1University of
Liège, Liège, Belgium; 2University of Ontario Institute of
Technology, Oshawa, ON Canada; 3University of Technology,
Sydney, Sydney, Australia
17:40 – 18:00 (L-01-15)
Chemical Blueprint of Extra Virgin Olive Oil
Giorgia Purcaro1; Chiara Cordero
2; Carol Bicchi
2; Lanfranco
Conte1,
1University of Udine, Udine Italy;
2University of Turin,
Turino, Italy
18:00 – 18:20 (L-01-16)
Advances in the Analysis of Olefin Monomers and Polymers by
Comprehensive Two Dimensional Gas Chromatography
(GC×GC)
William Winniford1; Anna Sandlin
1; James Griffith
1; Kefu Sun
1;
Jim Luong2; Rob Edam
3; W. Christopher Siegler
1; Patric Eckerle
4,
1Dow Chemical, Freeport, TX USA;
2Dow Canada, Fort
Saskatchewan, AB, Canada; 3Dow Benelux, Terneuzen, The
Netherlands; 4Dow Deutschland, Rheinmuenster, Germany
18:20 – 18:40 (L-01-17)
Development of Nitrogen Chemiluminescence as a Powerful
Detector for GC×GC
Jacqueline Hamilton1; Mustafa Z. Özel
1; Noelia Ramirez
1; Alastair
C. Lewis2; Emanuela Finessi
1;
1University of York, York, United
Kingdom; 2NCAS, University of York, York, United Kingdom
19:00 – 22:00 Symposium Event – Free and Open to All Attendees
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Tuesday, May 14, 2013
08:00 – 17:20 Registration in the Ballroom Foyer
08:30 – 14:00 See ISCC Program for Schedule – Page 87
14:00 – 15:30 Poster Session – Visit the Exhibitors and Posters in the Foyer and
Pasadena, Sierra and Ventura Ballroom
Phillips Award Lecture in the Catalina and Madera Ballrooms Session Chair: Jean-Marie Dimandja, Spelman College, Atlanta, GA USA
15:30 – 16:00 (L-02-06)
Revolution of Hydrocarbons Analysis by Comprehensive Two-
dimensional Gas Chromatography: The Never Ending Story
Thomas Dutriez1; Ward D’Autry
1; Jeroen Knooren
1; Gerard
Kwakkenbos1; John Mommers
1,2,
1DSM Resolve, Geleen, The
Netherlands; 2University of Amsterdam, Amsterdam, The
Netherlands
GC×GC Applications II in the Catalina and Madera Ballrooms Session Chairs: Hans-Gerd Janssen, Unilever, Vlaardingen, The Netherlands
and Peter Tranchida, University of Messina, Messina Italy
16:00 – 16:20 (L-02-07)
Identifying Biomarkers of P. aeruginosa Antibiotic
Susceptibility Using GC×GC-TOFMS and Fisher Ratios
Heather Bean1; Jean-Marie D. Dimandja
2; Jane E. Hill
1;
1University of Vermont, Burlington, VA USA;
2Spelman University,
Atlanta, GA USA
16:20 – 16:40 (L-02-08)
The Analysis of Halogenated Organics in Environmental
Samples Using Comprehensive Two-Dimensional Gas
Chromatography (GC×GC) Alina Muscalu
1; Karl Jobst
1; Tony Chen
1; Gerry Ladwig
1; Li
Shen1; Eric Reiner
2; Dave Morse
1,
1Ontario Ministry of the
Environment, Toronto, ON Canada; 2University of Toronto,
Toronto, ON Canada
16:40 – 17:00 (L-02-09)
Simultaneous Analysis for Complex PAH Mixtures Using
Novel Column Combinations in GC×GC/TOF-MS Eunha Hoh
1; Carlos Manzano
2; Staci Massey Simonich
2,
1San
Diego State University, San Diego, CA USA; 2Oregon State
Universiy, Corvallis, OR USA
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Tuesday, May 14, 2013 continued…
17:00 – 17:20 (L-02-10)
Taking a Good Dose of High Separation Medication for Gas
Chromatography Analysis of Fatty Acid Methyl Esters Philip Marriott; Annie Zeng; Asia Nosheen; Yada Nolvachai;
Blagoj Mitrevski; Sung-Tong Chin, Monash University, Clayton,
Australia
17:20 – 17:30 Closing Comments and Poster Award Announcements
Philip Marriott, Monash University, Clayton, Australia
17:30 – 19:00 Exhibitor Reception – Visit the Exhibitors in the Ballroom Foyer
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L-01-01
GC×GC: In Hot Pursuit of More Chemical Information
Robert E. Synovec
University of Washington, Seattle, WA USA
GC x GC was pioneered by John Phillips and co-workers in the early 1990’s. My lecture
begins at this stage, when I had the opportunity to visit with John and hear him talk about
his ground breaking research on thermal modulation. Since my group was focusing our
efforts on LC and sensors in the early 1990’s, we could not immediately make the jump
into the GC x GC arena. But the pull of this emerging technology was too strong!
Just a few years later my group began our own work in this exciting area, with a keen
interest in making an impact in three arenas: instrumentation development, applications,
and data analysis. Our main research thrust was, and continues to be, in developing and
applying GC x GC to tackle existing and emerging challenges in chemical analysis. Our
instrumentation development is aimed at theoretically understanding how to optimize
peak capacity production, for both thermal modulation and valve modulation instrument
designs, and then to experimentally produce data with the optimized performance.
Recently we have experimentally obtained a peak capacity of 6000 peaks in GC x GC -
TOFMS separations of only 7 minutes, providing a 10-fold improvement in peak capacity
production compared to standard practice. Our efforts in developing and applying data
analysis tools are aimed at utilizing chemometric software to glean useful information
from the GC x GC data. Notably, we have developed Fisher Ratio software for discovery
based analyses (eg., metabolomics, forensics, and fuels), and PARAFAC software for
robust and accurate deconvolution of the analytes from overlapping peaks.
In this lecture I intend to provide insight into why GC x GC is an exciting and useful field
for a wide range of studies. Thoughts on future research directions to increase the
generation of useful chemical information will be provided.
Notes:
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L-01-02
Using a Simple Selectivity Model to Design Better GC×GC Separations
John Seeley1; Abhijit Ghosh
1; Stacy Seeley
2
1Oakland University, Rochester, MI USA;
2Kettering University, Flint, MI USA
Separating a specific group of analytes from sample matrix components is the goal of
many GC×GC analyses. Twenty years of published GC×GC studies have shown that
column combinations can often be found that eliminate, or at least minimize, the overlap
between analytes and interfering compounds. However, other than directly testing
numerous combinations of stationary phases, there is little published insight on how to
identify promising phase combinations ahead of time. Instead, the common advice is to
maximize the orthogonality of the separation. This guidance is ambiguous and often
misleading.We have developed a simple model of GC×GC selectivity that can aid in
identifying promising GC×GC stationary phase combinations. This model is an
adaptation of the solvation parameter model originally introduced by Abraham and
further developed by Poole. Past studies have shown that this model can accurately
predict the relative GC×GC retention of a wide range of compounds. In this study, we
further demonstrate the ability of the solvation parameter model to design a successful
GC x GC separation of cyclic siloxanes from a diverse set of potential sample matrix
components. The effectiveness of the stationary phase combination was experimentally
validated by isolating and quantifying siloxanes in biogas samples.
Notes:
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L-01-03
Separation and Identification of 'Supercomplex' Mixtures of Toxic Organic Acids
by GC×GC-High Resolution-MS with Ionic Liquids: a 'Hump' No More!
Steven Rowland
Plymouth University, Plymouth, United Kingdom
The mixtures of organic compounds found in petroleum and oil sands have been called
‘supercomplex’ Amongst these, carboxylic acids known as naphthenic acids exist as
thousands of unknown compounds. The mixtures have proved to have a variety of
toxicological effects on a range of organisms, so they are important environmental
contaminants.
GC×GC has proved to be one of the few methods capable of partially resolving such
complex mixtures-once the acids have been converted to esters-but until recently,
published electron ionisation mass spectra were rather uninformative due partly to non-
optimisation of the separations.
We have therefore spent some time optimising the conditions for separating such
mixtures (or chromatographic ‘humps’) by GC×GC, using a variety of stationary phases,
including ionic liquids. By GC×GC-MS we obtained good quality, library-searchable,
nominal and accurate mass, spectra of thousands of C10-30 compounds in the toxic
mixtures. To confirm some of the identities we synthesised numerous of the acids and
then measured the toxicities of the individual compounds.
Examples of acids identified to date with authentic compounds for confirmation included,
the ‘diamondoid’, adamantane and diamantane-type acids and even aromatic acids such
as dehydroabietic acid, which were previously not considered to be naphthenic acids.
GC×GC- high resolution MS was then used to confirm, modify or refute some previously
suggested acid structures and to assign numerous diaromatic sulfur-containing acids,
which were confirmed by GC×GC-sulfur chemiluminescence detection.
Sub-fractionation of the esters of the acids by argentation solid phase extraction,
argentation HPLC and preparative GC and GC×GC has allowed us to isolate even
individual acids. Toxicity assays of the sub-fractions have allowed us to study the
lethality and estrogenic effects of these sub-fractions to freshwater fish.
Notes:
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L-01-04
GC×2GC and 2GC×GC Using Contra-directional Thermal Modulation
Benjamin Savareear1; Laura Tedone
2; Robert Shellie
1
1ACROSS, University of Tasmania, Hobart, Australia;
2 University of Messina, Messina,
Italy
In 2012 at Riva del Garda, we introduced a multiplexed, dual-second dimension column,
comprehensive two-dimensional GC approach that splits the first-dimension column
effluent into two second-dimension columns with different stationary phases. Effluent
from the two second-dimension columns is recombined before detection using a single
detector. Contra-directional modulation and careful manipulation of the Leco quad-jet
GC×GC modulator timing parameters facilitates this approach without any need for
instrument modification.
This approach has been explored further and our investigations have led to serendipitous
development of a novel 2GC×GC analysis approach. Our 2GC×GC approach also relies
on contra-directional modulation. The 2GC×GC approach allows use of multiple linear
retention indices to assist compound identification, but only employs a single second-
dimension column and one detector.
We will discuss the concept of contra-directional modulation covering genesis,
development, and application to characterization of essential oil.
Notes:
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L-01-05
Hybrid Comprehensive Two-Dimensional - Multidimensional Gas Chromatography
(GC×GC-MDGC): Potential and Applications
Blagoj Mitrevski; Leesun Kim; Philip Marriott
Monash University, Clayton, Australia
Multidimensional gas chromatography (MDGC) and comprehensive two-dimensional
gas chromatography (GC×GC) both stem from classical one dimensional GC, and offer
expanded separation performance. They both have found particular niche applications,
rather complementing each other than competing. Recently, we have developed a new
approach where the two techniques are effectively combined in an automated hybrid
GC×GC-MDGC system. The hybrid system comprises a 3-column separation
arrangement. The heart-cut process (MDGC) samples peaks into the 3rd
column, and is
applied to targeted regions from a GC×GC modulated chromatogram.
The 2D GC×GC plot aids selection of appropriate regions, so the H/C intervals are
located within the GC×GC modulation period. Quantitative effluent flow diversion and
H/C of targeted compounds has been obtained for zones as short as 1 s on the second
dimension column.
The method was successfully applied to single targeted components such as coffee
volatiles, allowing just these few compounds to be excised and analysed out of a very
complex sample. In addition a band of components (oxygenates in algae-derived fuel)
can be completely isolated from matrix interferences for further separation on the 3rd
dimension long column. Recent results show that the approach can be applied also for
targeted compounds diversion to a separate channel (sulfur speciation in shale oil on
FPD), or for isolation, cryo-trapping and collection of targeted individual components
(dimethylnaphthalenes) for further spectroscopic analysis (i.e. NMR). Potential future
applications will also be discussed (i.e. in odour analysis).
Notes:
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L-01-06
Optimization Aspects in Comprehensive Two-Dimensional Gas Chromatography
Tadeusz Gorecki; Ahmed Mostafa; Matthew Edwards
University of Waterloo, Waterloo, ON Canada
Comprehensive two-dimensional gas chromatography (GC×GC) was introduced over
two decades ago. It quickly established itself as one of the most powerful and effective
techniques for the characterization of complex mixtures of volatile and semi-volatile
compounds. The power of GC×GC comes from the use of two different separation
mechanisms acting on all components of a sample. This is accomplished by using two
chromatographic columns of orthogonal selectivity, connected in series through a special
interface known as the modulator. The role of the modulator is to periodically trap and/or
sample the primary column effluent and inject it into the secondary column at regular
intervals. Sample components that coelute at the outlet of the first column can thus be
separated in the second column. This results in enhanced separation with greatly
improved peak capacity. In addition, structured chromatograms are typically generated
when compounds belonging to homologous series are present in the sample. However,
method optimization in GC×GC can be difficult and time-consuming because most
adjustable parameters interact with each other. The presentation will focus on the
optimization of the main operational parameters in GC×GC. Consideration will be given
to aspects such as stationary phase chemistries, column dimensions, carrier gas flow,
temperature programs, as well as modulation and detection settings. New developments
in the area of modulation, including the design of powerful single stage thermal
modulators requiring no consumables, will also be presented.
Notes:
25
L-01-07
Optimization of Column Formats and Flow Conditions in GC×GC
Hans-Gerd Janssen1, 2
; Daniela Peroni2
1Unilever Research, Vlaardingen, The Netherlands;
2University of Amsterdam,
Amsterdam, The Netherlands
Important parameters in the selection of the second dimension (2D) column in GC×GC
are the selectivity and the speed of this column. Ideally, the 1D and 2D columns should
be orthogonal. In addition to this, the 2D column should be sufficiently fast to allow the
analysis of some 3 to 4 fractions across each 1D peak. To obtain this high speed, short
narrow-bore columns are generally used in the 2D, as opposed to the long normal-bore
1D columns. Due to these differences in column dimensions optimum-velocity operation
cannot be obtained in both dimensions simultaneously. At high flow rates the 1D column
is in the optimum, but the 2D column is above optimum. Alternatively, at low flow rates
the 2D column is in its optimum, but now the 1D column is operated at too low a
velocity. Clearly approaches where optimum performance is obtained in both dimensions
simultaneously would be desired.
In the current presentation we will described methods to better balance the relative
analysis speeds in the two dimensions of a comprehensive GC×GC set-up. Methods to do
so include the use of multiple parallel columns or of monolithic columns in the 2D. An
alternative approach is also described. Theoretical calculations will be shown that
demonstrate that the use of higher 2D outlet pressures, i.e. higher detector pressures, can
also be a route towards simultaneous optimum velocity operation. The hard-ware
required to do so is simple: it consists of a simple column outlet restrictor only. Methods
to construct such restriction devices will be shown. Finally, the improved performance of
these higher outlet-pressure systems will be demonstrated using plate height
measurements and examples of real separations. A significant gain in peak capacity is
obtained in these systems, but unfortunately only at the expense of an increase in analysis
time.
Notes:
26
L-01-08
Gas Velocity at the Point of Re-Injection: An Additional Parameter in
Comprehensive 2D GC Optimization
Peter Tranchida1; Luigi Mondello
1, 2
1SCIFAR, University of Messina, Messina, Italy;
2C.I.R., Campus Bio-Medico, Roma,
Italy
The present research is focused on the introduction of a new optimization parameter in
the field of comprehensive 2D GC (GC×GC), herein defined as “gas velocity at the point
of re-injection”. GC×GC experiments were performed using a loop-type modulator and a
rapid-scanning quadrupole mass spectrometer, as detection system. All experiments were
performed using a 30 m x 0.25 mm ID apolar primary column, and a 1 m x 0.10 mm ID
medium-polarity secondary one. With regards to the modulator loops, three types of
uncoated columns were used, namely with a 0.25, 0.18, and 0.10 mm ID. It was found
that under the same second-dimension analytical conditions (modulation, oven
temperature, gas velocity) the quality of the GC×GC separation was dependent on the gas
velocity at the moment of re-injection. For a loop-type modulator, the re-injection point is
located at the downstream cooling/heating point of the delay loop. It was found that the
GC×GC performance gradually improved when the ID of the modulator loop decreased
(and the re-injection gas velocity increased), and reached its best when the 0.10 mm ID
uncoated column was used. GC×GC experiments were performed on a C14 n-alkane (to
evaluate the efficiency of band re-injection), on fatty acid methyl esters and on an
essential oil sample (to evaluate the overall separation performance). The results herein
reported can be considered as a contribution towards the full optimization of GC×GC
processes and are valid for practically any type of cryogenic modulator.
Notes:
27
L-01-09
Use of Multidimensional Retention Normalization in Predictive GC×GC for Column
Set Selection and Separation Optimization
Jean-Marie Dimandja
Spelman College, Atlanta, GA USA
Column selection in GC×GC has primarily been done on the basis of empirical reviews
of previously attempted stationary phase combinations rather than through the use of a
quantifiable metric. As a result, the majority of GC×GC separations are performed on
two primary types of column sets: the conventional orthogonality set (non-polar/semi-
polar) and the “reversed phase” orthogonality set (polar/non-polar). Efforts to develop
predictive models of GC×GC chromatograms have proven to be very time consuming,
and are unlikely to be adopted for routine operation in the majority of application
development laboratories even though the results of the predictive strategies have been
adequate in proof-of-concept studies.In this work we explore the use of a simple
predictive method for column selection that is based on the use of normalized
information (in the form of indexed retention values) obtained from single dimension gas
chromatographic columns. The predictive chromatograms are two-dimensional plots in
which the first dimension axis is the retention index of the analytes on the primary
column, and the second dimension axis is the retention index difference (δI) of each
analyte between the secondary column and the primary column. An ensemble of
predictive chromatograms can thus be quickly generated on a multitude of column
combinations, and then evaluated on the basis of factors such as peak separation density
and the number of separated peaks. The presentation will go over the details of the
predictive GC×GC chromatogram generation, and will compare these predictive results
to actual column sets demonstrate the quality of the model to real data for a sample set of
over 60 residual solvents.
Notes:
28
L-01-10
gc×GC: The Importance of Second Dimension Column Length in Promoting True
Peak Capacity Increase Comprehensive Two-Dimensional Gas Chromatography
Jack Cochran1; Michelle Misselwitz
1; Julie Kowalski
1; Mark Merrick
2
1Restek Corporation, Bellefonte, PA USA;
2LECO Corporation, St. Joseph, MI USA
GC×GC is considered (and even promoted) by some practitioners as being a very
complex technique where many parameters need optimization before a successful
analysis can be accomplished. This partially arises because a one-dimensional GC
analysis requires consideration of column choice, carrier gas type and flow rate, inlet
parameters, GC oven programming, and detector type and operation. In its simplest
iteration then, all of those parameters are now multiplied by two (the GC×GC modulator
is the second inlet) for GC×GC, except there is only one detector in most applications.
We realize that most GC×GC users will start with a 30m x 0.25mm x 0.25µm first
dimension column, since it is the most common format for analysis of semivolatile
compounds and is widely appropriate for many sample types in one-dimensional analysis
because of its relatively good separating power, sample loading capacity, and analysis
time. Using simple flow and oven programming rules, it is possible to maximize peak
capacity for this column, leading to well-defined first dimension peak widths such that
second dimension column length can be easily calculated based on desired modulation
time. For true peak capacity increase GC×GC, that means at least 3 modulations per first
dimension peak width. We will demonstrate not only the positive effects of this
approach, but also the detrimental effects that occur when having too long of a second
dimension column, which unfortunately is still common practice in GC×GC today. We
will also give very simple method development guidelines that allow anyone to become a
GC×GC expert.
Notes:
29
L-01-11
Application of Comprehensive Two-Dimensional Gas Chromatography to the
Analysis of Volatile Compounds of Brazilian Wines
Juliane E. Welke1; Marcelo Lazzarotto
3; Vitor Manfroi
2; Mauro Zanus
3; Cláudia Zini
1
1Instituto de Química;Porto Alegre, Brazil
2Instituto de Ciência e Tecnologia de
Alimentos, Universidade Federal do Rio Grande do Sul, Porto Alegre, Brazil; 3Embrapa
Uva e Vinho, Bento Gonçalves, Brazil
Wines produced in the South part of Brazil represent 90% of the Brazilian wine
production and represent also a considerable social and economic impact in this region,
although knowledge related to wine characteristics is scarce. A better understanding of
Brazilian wine characteristics is necessary, as the wine industry seeks further
improvement of wine quality, processes and also wants to reach denomination of origin.
Wine aroma is the result of complex interactions among vineyard geographical location,
grape variety, yeast strain, and technical conditions of wine-making. There are evidences
of relationships among the volatile fraction of beverages and several aspects, such as raw
material, process of production, etc. One-dimensional gas chromatography with mass
spectrometric detector (1D-GC/MS) is usually the analytical technique employed for the
analysis of wine volatiles; however the use of comprehensive two-dimensional gas
chromatography with time-of-flight mass spectrometric detection (GC×GC/TOFMS) has
already shown advantages over the 1D technique for complex samples, even though it has
had a limited use for wine volatiles until now. The application of solid phase
microextraction and GC×GC/TOFMS along with statistical tools such as Fisher ratio and
principal component analysis to several varietal Brazilian wines (Cabernet Sauvignon,
Merlot, Chardonnay, Sauvignon Blanc and Pinot Noir) and also to sparkling wines
(Moscatel and Champenoise) has been performed. GC×GC/TOFMS provided a higher
number of components and also unveiled several coelutions of aroma active compounds
in the first and/or second dimension, providing a more detailed knowledge about
components that may contribute to wine aroma. Chemometric treatment proved to be a
useful tool for reducing GC×GC data to the most important components for
differentiation among different varietal wines and between base and sparkling wines and
may be employed in future studies to find markers of variety, product or process quality
or even to contribute to the achievement of denomination of origin.
Notes:
30
L-01-12
Evaluation of GC - Online Reduction x GC for the Separation of Fatty Acid Methyl
Esters
Pierluigi Delmonte; Ali Reza Fardin Kia; Jeanne I. Rader
FDA, College Park, MD USA
The common strategy in the development of GC x GC separations of fatty acid methyl
esters (FAME) is coupling 2 mono-dimensional separations characterized by a high
degree of orthogonality: a low polarity column is generally preferred for 1D and a
medium/high polarity column for 2D. FAMEs differ among each other primarily in their
chain length, their number of unsaturations, and the cis/trans configuration of their double
bonds. In this study, the two dimensional separation of FAMEs is achieved by using two
identical highly polar separation columns, but the analytes are chemically modified
between the two dimensions of separation. FAMEs are reduced to their fully saturated
forms during passage through a capillary tube coated with palladium in the presence of
hydrogen carrier gas. The products of the reaction, which are saturated FAMEs, are then
separated based on their chain lengths. When the chromatographic system is operated
under isothermal conditions, saturated FAMEs lie on a straight diagonal line bisecting the
separation plane, while FAMEs with the same carbon skeleton but different number,
geometric configuration or position of double bonds lie on lines parallel to the 1D time
axis. FAMEs with the same chain length are eluted on crescents when the
chromatographic system is operated under a temperature program, and the modulation
time can be reduced to 2 s or less. This technique allows the separation of trans fatty
acids and polyunsaturated FAMEs in a single analysis by eliminating the overlap between
the FAMEs with different chain lengths.
Notes:
31
L-01-13
Extending the Orthogonality to the Whole Analytical Process: Does it Open New
Perspectives in Flavoromics?
Chiara Cordero; Cecilia Cagliero; Erica Liberto; Luca Nicolotti; Patrizia Rubiolo;
Barbara Sgorbini; Carlo Bicchi
University of Turino, Turino, Italy
Modern omics disciplines (metabolomics, foodomics, flavoromics etc..) include in their
investigations all constituents considered collectively (primary and secondary
metabolites, compounds generated by thermal treatments and/or enzymatic activity) [1]
and represent the route of choice for a comprehensive evaluation of food attributes where,
in particular, sensory properties are unequivocally correlated to a specific and peculiar
quali-quantitative distribution of known (or unknown) chemicals [2]. Flavor research
profitably exploits the potentials of -omic approaches and two-dimensional
comprehensive gas chromatography coupled to mass spectrometric detection (GC×GC-
MS) represents the technique of choice for a comprehensive investigation of the aroma
fingerprint of complex food samples. However, to maximize the information content for
every single run, suitable sampling strategies and sample preparation approaches, should
be designed and implemented.
This study presents experimental results of a flavoromic study aiming to reveal the aroma
and technological blueprint of complex food samples, in particular, the advantages of a
true multidimensionality, from sample preparation (direct sampling, orthogonal sampling,
selective sampling, high concentration capability sampling) to separation (GC×GC and
GC×GC-MS) will be emphasized and new perspectives discussed.
1. Herrero M, Simõ C, García-Cañas V, Ibáñez E, Cifuentes A. (2012) Mass
Spectrometry Reviews, vol. 31(1):49-69
2. Christlbauer M, Schieberle P. (2009) Journal of Agricultural and Food Chemistry vol.
57(19):9114-22
Notes:
32
L-01-14
TD-GC×GC-TOFMS Study of Human Cadaveric VOC Profiles
Pierre-Hugues Stefanuto1; Sonja Stadler
2; Romain Pesesse
1; Kayte Perrault
3; Shari
Forbes3; Jean-Francois Focant
1
1University of Liège, Liège, Belgium;
2University of Ontario Institute of Technology,
Oshawa, ON Canada; 3University of Technology Sydney, Sydney, Australia
Human remain detection (HRD) canines are commonly used to locate or trace cadavers,
but also to assist in recovering victims of natural disasters. Some artificial scent solutions
are available for training purposes, but what dogs are generally educated with are
oversimplistic solutions1. A better understanding of the volatile organic compound
(VOC) profile released by death or injured bodies could possibly help better design of
training solutions for forensic purposes.
In previous studies, we developed direct-sampling based approaches for cadaveric VOC
analysis from grave soils and decaying bodies by mean of thermal desorption (TD)
coupled to comprehensive two-dimensional GC coupled to time-of-flight MS (GC×GC-
TOFMS) 2,3,4
. They were based on the use of human analogs (Sus domesticus L.
carcasses).
For the present study, we investigated the VOC profile of early stage decomposition of
human bodies. We analyzed samples collected during different trials organized during
different seasons in a body farm located in Texas. Samples included environmental
controls, pig carcasses, and human bodies (protected or not from scavenger insects). The
data processing was performed in the light of identifying possible seasonal and species
variations. Both peak capacity enhancement and spectral deconvolution helped to
characterize VOC mixtures and improve comparisons of profiles.
Acknowledgements: Human samples were collected during the project ‘Development and
validation of standard operating procedures for measuring microbial populations for
estimating a post-mortem interval’ Grant Award No. 2010-DN-BX-K243. The authors of
that grant are acknowledged for giving us the opportunity to access cadavers for
sampling.
1. Stadler, S. et al. J Chromatogr A (2012) 1255, 202-206.
2. Brasseur C. et al. J Chromatogr A (2012) 1255, 163-170.
3. Dekeirsschieter, J. et al. PLoS ONE(2012) 7, e39005.
4. Stadler, S. et al. Anal Chem (2013)85, 998-1005.
Notes:
33
L-01-15
Chemical Blueprint of Extra Virgin Olive Oil
Giorgia Purcaro1; Chiara Cordero
2; Carlo Bicchi
2; LanfrancoConte
1
1University of Udine, Udine, Italy;
2University of Turino, Turino, Italy
Comprehensive two-dimensional gas chromatography (GC×GC) can be considered a
mature technique to be adopted as a routine control technique in the food quality
assessment process. The advantages mostly rely on the possibility to contemporarily
perform detailed and sensitive targeted and un-targeted profiling of samples. In the
present work the volatile fraction of a series of extra virgin olive oil samples has been
characterized by coupling conventional and advanced headspace sampling techniques
(Static Headspace - S-HS, Solid Phase Microextraction - HS-SPME and Headspace
Sorptive Extraction - HSSE) with GC×GC-MS. Complex 2D patterns, including
hundreds of potentially informative compounds, have been adopted for samples’
classification (similarities and differences) thus, discriminating analytes and known key-
aroma compounds, have been quantified through reliable and sensitive headspace
sampling approaches. Samples’ sensory attributes, and in particular specific aroma
defects responsible of samples declassification, defined by an official Panel test, have
been combined with the GC×GC aroma blueprint to establish correlations and locate
informative markers to be profitably screened in a routine quality assessment.
Notes:
34
L-01-16
Advances in the Analysis of Olefin Monomers and Polymers by Comprehensive Two
Dimensional Gas Chromatography (GC×GC)
William Winniford1; Anna Sandlin
1; James Griffith
1; Kefu Sun
1; Jim Luong
2; Rob
Edam3; W. Christopher Siegler
1; Patric Eckerle
4
1Dow Chemical, Freeport, TX USA;
2Dow Canada, Fort Saskatchewan, AB Canada;
3Dow Benelux, Terneuzen, The Netherlands;
4Dow Deutschland, Rheinmuenster,
Germany
Comprehensive two-dimensional gas chromatography is now more than 20 years old and
many advances have been made, particularly in the last 10-12 years. But this is far from
a mature technique owing to the wide range of experiments that can be designed with
regards to sample introduction, column selection and detection. The quality of results
that can be obtained now are far better than the early examples that were done with first
generation cryogenic modulators and primarily apolar/polar column combinations. The
breadth of samples that can now be addressed is exemplified by analysis of olefin
monomers and polymers. They are the most widely used polymers in the world and
represent one of the largest revenue streams in the chemical industry worldwide. On one
extreme are monomers such as ethylene and propylene which are extremely difficult to
focus with cryogenic modulation. The other extreme is the separation of higher
oligomers either directly or via pyrolysis, limited primarily by the stability of the columns
at high temperatures. Examples of information that can be obtained include: catalyst
poisons in monomers, isomerization of comonomers, catalyst characteristics, polymer
additives and polymer microstructure. The focus of this presentation is to demonstrate
how the recent advances in GC x GC have improved the analyses of diverse sample types
from the production of olefin polymers and highlight opportunities for further impact.
Notes:
35
L-01-17
Development of Nitrogen Chemiluminescence as a Powerful Detector for GC×GC
Jacqueline Hamilton1; Mustafa Z. Özel
1; Noelia Ramirez
1; Alastair C. Lewis
2; Emanuela
Finessi1
1
University of York, York, United Kingdom; 2NCAS, University of York, York, United
Kingdom
The main advantage of GC×GC is the impressive amount of resolution that can be
achieved. When samples are extremely complex, such as petrochemical or
environmental samples, even this improved separation power can be insufficient to
isolate all the minor components. Organic nitrogen compounds (ON) are often present in
very low levels in these samples and are difficult to isolate. However, they are often
some of the most toxic and carcinogenic components. In addition, ON plays a key role in
the Earths N-cycle, which has increased by over 100 % as a result of human activities.
Thus there is a real need for a technique that provides a highly sensitive and highly
selective technique to measure ON in a range of samples.
We have developed a sensitive and quantitative method for ON using GC×GC coupled to
a nitrogen chemiluminescence detector (GC×GC-NCD). The instrument shows high
selectivity for ON, thus removing the interference from the organic C matrix. It gave an
equimolar response for most organic nitrogen species investigated, which allows the
quantification of the total ON content of samples even where the exact molecular
structure was unknown or standards were not available. Limits of detection were
determined to be in the range 0.16-0.27 pgN.
The GC×GC-NCD has been used in a range of applications to investigate ON and these
will be presented. It has been used to study the formation and composition of ON in
environmental samples including atmospheric aerosols, rainwater and river water. It has
also allowed us to measure toxic ON compounds in house dust in smokers and non-
smokers homes and thus estimate the carcinogenic risk of ingestion and skin exposure in
children and adults. Preliminary results showed that the estimated cancer risk exceeded
recommended thresholds in some households. Other applications include food chemistry
and engine lubricant degradation studies.
Notes:
36
L-02-06
Revolution of Hydrocarbons Analysis by Comprehensive Two-Dimensional Gas
Chromatography: The Never Ending Story
Thomas Dutriez1; Ward D’Autry
1; Jeroen Knooren
1; Gerard Kwakkenbos
1; John
Mommers1, 2
1DSM Resolve, Geleen, The Netherlands;
2University of Amsterdam, Amsterdam, The
Netherlands
Hydrocarbon (HC) matrices, e.g. feedstocks, process effluents and commercial products,
are among the most complex matrices in the world. Since the introduction of GC×GC by
Phillips and Liu, petrochemical companies have shown great interest in this breakthrough
technique by supporting not only instrumental and method developments, but also new
theoretical and practical methodologies. Why this interest? Owing to the fantastic
separation power of GC×GC combined with robust quantification capabilities. Current
day, GC×GC is globally implemented in HC R&D labs and seems to be mature for
screening selective group typing, molecular characterization or target analysis of HC
matrices. However, as a result of sample complexity, a lot of improvements can still be
performed by “revolutionizing” separation and detection in order to challenge current
high-end techniques like FT-ICR-MS.
Notes:
37
L-02-07
Identifying Biomarkers of P. aeruginosa Antibiotic Susceptibility Using GC×GC-
TOFMS and Fisher Ratios
Heather Bean1; Jean-Marie D. Dimandja
2; Jane E. Hill
1
1University of Vermont, Burlington, VA USA;
2Spelman University, Atlanta, GA USA
A primary cause of morbidity and mortality for Cystic Fibrosis (CF) patients is chronic
Pseudomonas aeruginosa lung infection. In the lung, P. aeruginosa acquires mutations
that allow it to persist in its new environment, including mucoid conversion, antibiotic
resistance, and quorum sensing deficiency, all of which have been correlated to poor
patient outcomes. We have observed that several highly-conserved CF-associated P.
aeruginosa mutations for these phenotypes create changes to the P. aeruginosa volatile
metabolome. Based on these data, we hypothesize that specific volatile biomarkers exist
for each mutation, making it possible to detect P. aeruginosa mucoidy, antibiotic
resistance, and quorum sensing deficiency in the lung using only the patient’s breath. Our
goals are to develop rapid tests to detect, track, and characterize P. aeruginosa infections
and mutations in situ in order to initiate early, targeted treatment, which is essential to
managing infection and maintaining healthy lung function in CF patients.In this work we
have identified putative biomarkers for the gene mexA, which impacts antibiotic
sensitivity, using comprehensive two-dimensional gas chromatography-time-of-flight
mass spectrometry (GC×GC-TOFMS) and Fisher ratio analysis (ChromaTOF Statistical
Compare). These putative biomarkers for mexA will be validated using P. aeruginosa
clinical isolates bearing this hallmark mutation for antibiotic sensitivity.
Notes:
38
L-02-08
The Analysis of Halogenated Organics in Environmental Samples Using
Comprehensive Two-Dimensional Gas Chromatography (GC×GC)
Alina Muscalu1; Karl Jobst
1; Tony Chen
1; Gerry Ladwig
1; Li Shen
1; Eric Reiner
2; Dave
Morse1
1Ontario Ministry of the Environment, Toronto, ON Canada;
2University of Toronto,
Toronto, ON Canada
Industrial chemicals have been used for more than 100 years in a wide variety of
applications such as solvents, precursors, reagents, surfactants, flame retardants and
pesticides. Over 100,000 chemicals are currently in use or present in consumer products
with over 30,000 considered to be in wide commercial use (>907kg/year) [1]. Many of
these compounds are halogenated, persistent, toxic and bioaccumulative and are detected
in all types of environmental matrices. The Stockholm Convention on persistent organic
pollutants (POPs) [2] targets only 12 compounds or compound groups including nine
organochlorine pesticides, polychlorinated biphenyls (PCBs) polychlorinated dibenzo-p-
dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) [3]. An additional nine
pesticides, flame retardants and surfactants were added in 2009 and three additional
compounds/groups: short-chain chlorinated paraffins (SCCPs), endosulfan and
hexabromocyclododecane are currently under review. The analysis of these compounds
requires numerous injections on multiple instruments. All of the Stockholm compounds
are halogenated compounds and the majority of them can be detected in a single
comprehensive two-dimensional gas chromatography (GC×GC) electron capture detector
(ECD) run with enhanced selectivity and sensitivity over single column methods. This
method can also be used to screen for additional halogenated organics in environmental
samples using ECD and mass spectrometry detection.
References
1. Muir DCG, Howard PH, (2006) Environ. Sci. Technol. 40:7157-7166
2. Stockholm Convention Secretariat (2001), UNEP, http//chm.pops.int,
3. Kannan N (2000), In: The Handbook of Environmental Chemistry (Vol.3), J.
Paasivirta (ed) Springer-Verlag, Heidelberg. 127-157
Notes:
39
L-02-09
Simultaneous Analysis for Complex PAH Mixtures Using Novel Column
Combinations in GC×GC/TOF-MS
Eunha Hoh1; Carlos Manzano
2; Staci Massey Simonich
2
1San Diego State University, San Diego, CA USA;
2Oregon State University, Corvallis,
OR USA
Separation of complex mixtures of polycyclic aromatic hydrocarbons (PAHs) using a
conventional one-dimensional GC/MS is difficult due to the high degree of overlap in
compound vapor pressures, boiling points and mass spectral fragmentation. Therefore,
the separation of PAH mixtures (including parent, alkyl-, nitro-, oxy-, thio-, chloro, and
bromo PAHs) requires multiple clean up procedures and fractions and instrumentation
runs. To improve the separation, we tested 2-D column combinations of non-polar, polar,
liquid crystal, and nano-stationary phase columns in GC×GC/ToF-MS. Also
environmental samples were tested for separation of the PAHs from matrix among the
column combinations. Overall, the highest chromatographic resolution and lowest
intereference from UCM and matrix were achieved using a 10m x 0.15mm x 0.10μm LC-
50 liquid crystal column in the first dimension and a 1.2m x 0.10mm x 0.10μm NSP-35
nano-stationary phase column in the second dimension. To evaluate each column
combination for its separation power, orthogonality was calculated using a method based
on conditional entropy that considers the quantitative peak distribution in the entire two-
dimensional space. The highest orthogonality was achieved for the combination of liquid
crystal and the nano-stationary phase columns, that was consistent with the best
separation for the PAH mixtures. This suggests that a column combination with higher
orthogonality is critical for generating greater separation power. In addition, the column
combinations were tested for quantitation of the PAH mixtures in SRM diesel particulates
and extract and the results were well matched with the certified values.
Notes:
40
L-02-10
Taking a Good Dose of High Separation Medication for Gas Chromatography
Analysis of Fatty Acid Methyl Esters
Philip Marriott; Annie Zeng; Asia Nosheen; Yada Nolvachai; Blagoj Mitrevski; Sung-
Tong Chin
Monash University, Clayton, Australia
Gas chromatography (GC) of fatty acid methyl esters (FAME) continues to exercise the
intellect of analysts, and exact a toll from those who seek to achieve maximum resolution
of this complex mixture of homologues, with their many isomeric variations. That FAME
are of importance to a broad interest area of the chemical sciences is a given - including
nutrition, plant and animal fats, cell constituents, and even in amniotic fluids. The
classical challenge to accomplish high resolution separation often relies upon a
combination of very (ultra-) long separation columns, and specialty (usually polar high
cyano-propyl content, and more recently ionic liquid) phases. But there have been
interesting and paradigm-confronting shifts in advances made in coupled column GC
methodologies. Whilst the first demonstration of GC´GC analysis of FAME was
conducted over 10 years ago, it seems that the message of the advantages of this approach
was not broadly adopted - perhaps not surprisingly.
Our efforts in this task were first reported in 2002 (Lipids, 37 (2002) 715). Both polar -
non-polar and non-polar - polar geometries were tested. In the meantime research
developed approaches incorporating ionic liquid phases. We have recently re-visited this
topic, and have also studied a range of ionic-liquid phases, integrated multidimensional
gas chromatography and GC´GC methods, investigation of comparative
performance of various highly-selective GC phases for typical FAME mixtures, and a
range of plant oils, and soil bacterial FAME. The search for fast and effective FAME
analysis continues.
Notes:
41
Application of GC×GC
to Pollution Studies
P-104-M
SPE-GC×GC-TOFMS for Detection of Disinfection By-Products and Endocrine
Disruptors in Municipal Water, Residential Swimming Pools, and Purified Bottled
Drinking Water John Heim; Joe Binkley; Jeff Patrick
LECO Corporation, St. Joseph, MI USA
P-105-M
Characterization of Adulterated Olive Oils in Cases of Food Fraud by
Comprehensive Two-Dimensional Gas Chromatography with Time-of-Flight
Mass Spectrometry (GC×GC-TOFMS) Elizabeth Humston-Fulmer; Joe Binkley
LECO, Saint Joseph, MI USA
P-106-M
A Compact Comprehensive Two-dimensional Gas Chromatography Approach for
the Analysis of Biogenic VOCs Samuel Edwards; Richard Lidster; Stephen Andrews; Alastair Lewis; Jacqueline
Hamilton; Chris Rhodes
The University of York, York, United Kingdom
P-110-M
GC×GC as a Powerful Tool for Quantitative Risk Assessment: Organic Nitrogen
Contaminants in House Dust, a Case Study Noelia Ramírez
1; Mustafa Z. Özel
1; Rosa Maria Marcé
2; Francesc Borrull
2; Alastair C.
Lewis3; Jacqueline F. Hamilton
1
1University of York, York, United Kingdom;
2University Rovira i Virgili, Tarragona,
Spain; 3NCAS, University of York, York, United Kingdom
42
Application of GC×GC
to Smoke and Residues
P-103-M
Use of GC×GC-MS in Discrimination of Accelerant Products in Forensic Cases –
Practical Case Report Thierry Ducellier; Guillaume Cognon; Audrey Junker; Bertrand Frere
French Gendarmerie (IRCGN), Rosny Sous Bois, France
P-107-M
Identification of New Markers of Wood Smoke Exposures in Firefighters Using
GC×GC-TOF-MS Brian McCarry
1; Sujan Fernando
1; Lorne Fell
2; David Alonso
2; Joe Binkley
2
1Department of Chemistry & Chemical Biology, Hamilton, ON Canada;
2LECO
Corporation, St. Joseph, MI USA
P-108-M
Evaluation of Dispersive and Cartridge Solid Phase Extraction Cleanups for Multi-
Residue Pesticides QuEChERS Extracts of Finished Tobacco with GC×GC-TOFMS Jack Cochran; Michelle Misselwitz; Julie Kowalski
Restek Corporation, Bellefonte, PA USA
P-109-M
Utilizing GC×GC - TOFMS to Improve the Data Quality for the Analysis of Fire
Debris Kari Organtini; Jessica Westland; Frank Dorman
The Pennsylvania State University, University Park, PA USA
P-114-T
Analysis of Mainstream Tobacco Smoke by SPME-GC×GC-TOFMS Michal Brokl
1; Louise Bishop
2; Christopher Wright
2; Chuan Liu
2; Kevin McAdam
2;
Jean-Francois Focant1
1University of Liège, Liège, Belgium;
2British American Tobacco, Southampton, United
Kingdom
43
Application of GC×GC
to Essential Oils and Related Techniques
P-102-T
Whole Oil Analysis Using Comprehensive Two-Dimensional Gas Chromatography
Coupled to Time-of-Flight Mass Spectrometry: A Powerful Tool for Sulfur
Speciation Bárbara Ávila
1; Vinícius Pereira
1; Alexandre Gomes
2; Débora Azevedo
1
1LAGOA-LADETEC, Instituto de Química, UFRJ, Rio de Janeiro, Brazil;
2CENPES,
Petrobras, Rio de Janeiro, Brazil
P-113-T
Volatile Composition of Agricultural Distillates of Different Botanical Origin by HS-
SPME/GC×GC-TOF-MS Paulina Biernacka
1; Waldemar Wardencki
2; Jacek Namieśnik
2; Tadeusz Górecki
1
1University of Waterloo, Waterloo, ON Canada;
2Gdańsk University of Technology,
Gdańsk , Poland
P-116-T
Comprehensive 2-Dimensional Gas Chromatographic Analysis of Cyclopia
(honeybush) Tea Volatile Compounds: Differentiation Between Species Using
Multivariate Statistics André de Villiers
1; Elizabeth Ntlhokwe
1; Jochen Vestner
2; Elizabeth Joubert
3; Nina
Muller3; Matthew Edwards
4; Tadeusz Górecki
4
1Department of Chemistry, Stellenbosch University, Stellenbosch, South Africa;
2Forschungsanstalt Geisenheim, Geisenheim , Germany;
3Department of Food Science,
Stellenbosch University, Stellenbosch, South Africa; 4University of Waterloo, Waterloo,
ON Canada
P-117-T
Analysis of Coffee Packaging and Filter Leachates from Various Single-Serve
Coffee Pod Suppliers Using GC×GC-TOFMS Cory Fix
1, 2; Joe Binkley
1, 2
1LECO Corporation, Las Vegas, NV USA;
2LECO Corporation, St. Joseph, MI USA
P-118-T
Improved Cis/Trans Fatty Acid Analysis of Edible Oils and Fats Using
Comprehensive GC×GC-FID Sjaak de Koning
1; Martijn Brandt
2; Herrald Steenbergen
2; Hans-Gerd Janssen
2, 3
1LECO Instrumente GmbH, Mönchengladbach, Germany;
2Unilever Research and
Development, Vlaardingen, the Netherlands; 3University of Amsterdam, Amsterdam, The
Netherlands
44
P-119-T
Comparison of Volatile Profiles of Base Wines and their Corresponding Sparkling
Wines Through Comprehensive Two-Dimensional Gas Chromatography Juliane Welke
1; Vitor Manfroi
3; Mauro Zanus
4; Marcelo Lazzarotto
2; Cláudia Zini
1
1Instituto de Química, UFRGS, Porto Alegre, Brazil;
2EMBRAPA Florestas, Colombo,
Brazil; 3Instituto de Ciência e Tecnol de Alimentos, UFRGS, Porto Alegre, Brazil;
4EMBRAPA Uva e Vinho, Bento Gonçalves, Brazil
P-136-M
Improvement of Comprehensive Two-Dimensional Gas Chromatography
Separations through Injection Port Backflushing Matthew Edwards; Julien Crepier; Tadeusz Górecki
University of Waterloo, Waterloo, ON Canada
45
Application of GC×GC
to Drug Analysis
P-120-T
Discovery-Based Analyses of Wastewater Samples for Characterization of Drug
Usage
Dr. Frank Dorman; Adrienne Brockman
The Pennsylvania State University, State College, PA USA
P-121-T
Analysis of Marijuana Street Samples for Simultaneous Potency and Trace Organic
Composition Using GC×GC-FID/ECD Frank Dorman
1; Amanda Leffler
1; Emily Ly
1; Jack Cochran
2; Julie Kowalski
2
1Penn State University, University Park, PA USA;
2Restek Corporation, Bellefonte, PA
USA
P-123-T
Comprehensive Gas Chromatography Coupled to Time of Flight Mass
Spectrometry in Doping Control: Evaluation of the Chromatographic Plane
Organization Aline C. de A. da Silva
1; Alessandro Casilli
1; Samantha S. Barbosa
1; Raphael S.F. Silva
2;
Monica C. Padilha1; Henrique Marcelo G. Pereira
1; Francisco R. Aquino Neto
1
1UFRJ, Rio de Janeiro, Brazil;
2IFRJ, Rio de Janeiro, Brazil
P-125-T
Discovery-based Analyses of Various Pharmaceuticals in Drinking Water Frank Dorman; Jordan Stubleski
The Pennsylvania State University, University Park, PA USA
46
Application of GC×GC
to Petrochemical Analysis
P-101-T
Evaluation of Two Sets of Columns for the Characterization of Bio-Oil of Sugar
Cane Straw Using Comprehensive Two-dimensional Gas Chromatography
Maria Elisabete Machado; Nathalia Kives; Marcelo Migliorini; Cláudia Zini; Elina
Caramão
Instituto de Química, UFRGS, Porto Alegre, Brazil
P-126-T
Recent Enhancements in Petrochemical Qualitative-to-Quantitative Workflow;
Employing GC×GC-TOF-MS for Rapid Method Development and Automated
Translation to GC×GC-FID Analysis Nick Bukowski; Steve Smith; Laura McGregor; Kurt Thaxton; Alun Cole
ALMSCO International, Llantrisant, United Kingdom
P-127-T
Advanced Hydrocarbon Characterization of Diesel Fuels Derived from Wide Range
of Feedstocks Rafal Gieleciak
1; Craig Fairbridge
1; William Cannella
2
1Natural Resources Canada, CanmetENERGY, Devon, AB Canada;
2Chevron
Corporation, Richmond, CA USA
P-128-T
A Beneficial GC×GC-TOFMS Procedure for Environmental Forensic
Fingerprinting Utilizing Structural Classifications to Differentiate Light Crude Oils John Heim; Joe Binkley; Liz Humston-Fulmer
LECO Corporation, St. Joseph, MI USA
P-129-T
Quality Control Measures for Robust GC×GC-SCD Analysis for Petroleum
Applications Jonathan Pierson; Wayne Rathbun; Paul Adams; Hung Pham
UOP, Des Plaines, IL USA
P-130-T
GC×GC as an Efficient Tool for High Throughput Tests in the Petroleum Industry:
A Case Study Vincent Souchon
1; Mélinda Tébib
1; Noémie Caillol
1; Frédéric Feugnet
2
1IFPEN - Physics and Analysis Division, Solaize, France;
2IFPEN - Process Design
Division, Solaize, France
47
P-131-T
Chemical Characterization of Neutral-acid Fractions from Bio-Oils by
Comprehensive Two-Dimensional Gas Chromatography Coupled to Time-of-flight
Mass Spectrometry Nathalia S. Tessarolo
1; Andrea Pinho
2; Alessandro Casilli
1; Débora A. Azevedo
1
1Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil;
2PETROBRAS/CENPES/Conversão de Biomassa, Rio de Janeiro, Brazil
P-132-T
Effectiveness Evaluation of Upgrading Processes of a Pyrolysis Oil by
Comprehensive Two-Dimensional Gas Chromatography Coupled to Time-of-Flight
Mass Spectrometry Raquel V S Silva
1; Alessandro Casilli
2; Gilberto Alves Romeiro
1; Debora Almeida
Azevedo2
1Universidade Federal Fluminense, Niterói, Rio de Janeiro;
2Universidade Federal do
Rio de Janeiro, Rio De Janeiro, Brazil
P-133-T
Application of Comprehensive Two-Dimensional Gas Chromatography with
Quadrupole Mass Spectometric Detection for Characterization of the Bio-Oil of
Sugar Cane Straw Jaderson Schneider; Michele da Cunha; Marcia Brasil; Cláudia Zini; Elina Caramão
Instituto de Química, UFRGS, Porto Alegre, Brazil
48
GC×GC Theory and Modulation Studies
P-135-M
Development, Optimization and Applications of a Consumable-Free Thermal
Modulator for Comprehensive Two-Dimensional Gas Chromatography Matthew Edwards; Tadeusz Górecki
University of Waterloo, Waterloo, ON Canada
P-137-M
High Speed Deans Switch for Comprehensive Two Dimensional Gas
Chromatography Abhijit Ghosh
1; Carly T. Bates
1; Stacy K. Seeley
2; John V. Seeley
1
1Oakland University, Rochester, MI USA;
2Kettering University, Flint, MI USA
P-139-M
A Pooled Sample Approach in Ethanol Fed Mice by GC×GC-TOFMS Utilizing
Standardized Methods and a Reference Feature for Biomarker Screening John Heim; David Alonso; Joe Binkley
LECO Corporation, St. Joseph, MI USA
P-140-M
Integrating GC×GC, (Ultra)High Resolution Mass Spectrometry and Mass Defect
Analysis for the Identification of Halogenated Contaminants in the Environment Karl J Jobst; Vince Y Taguchi; Trudy Watson-Leung; Dave Poirier; Paul A. Helm; Eric J
Reiner
Ministry of the Environment, Toronto, ON Canada
P-141-M
Sample Preparation, Comprehensive Two-Dimensional Gas Chromatography and
Customized Data Mining for Biomarker Investigation in Geochemical Samples - a
Case Study Elaine Marotta; Alessandro Casilli; Maria Regina Loureiro; Débora Azevedo; Francisco
Aquino Neto
LAGOA-LADETEC, Instituto de Química, UFRJ, Rio de Janeiro, Brazil
P-142-M
Temperature-Tunable Selectivity in Comprehensive Two-dimensional Gas
Chromatography John Mommers
1, 2; Thomas Dutriez
1; Giulia Pluimakers
3; Jeroen Knooren
1; Sjoerd van
der Wal1, 2
1DSM Resolve, Geleen, The Netherlands;
2University of Amsterdam, Amsterdam, The
Netherlands; 3Avans Hogeschool, Hertogenbosch, The Netherlands
49
P-143-M
Quantitative Comparison of Multiple Integration Methods for Determing Mass
Fractions of Polycyclic Aromatic Hydrocarbons in Complex Samples Using GC×GC Jacolin Murray; Benjamin Place; Michele Schantz
NIST, Gaithersburg, MD USA
P-144-M
Improvement of the Measurement Efficiency by Fast-GC×GC-HRTOFMS Method Jun Onodera
1; Masaaki Ubukata
2; John Dane
2; Akihiko Kusai
1
1JEOL Ltd., Akishima Tokyo, Japan;
2JEOL USA, Inc., Peabody, MA USA
P-145-M
Application of Visual Basic (VB) Scripting and Comprehensive GC/TOF for the
Identification of New Halogenated Contaminants in Norwegian Ambient Air Laura Röhler
1, 2; Roland Kallenborn
1, 3; Martin Schlabach
2
1IKBM, Norwegian University of Life Sciences, Aas, Norway;
2NILU, Norwegian Institute
for Air Research, Kjeller, Norway; 3UNIS, The University Centre in Svalbard,
Longyearbyen, Norway
P-146-M
Utilization of a Comprehensive Reverse Fill/Flush Flow Modulated GC×GC-
FID/MS Instrument to Simultaneously Enable Analyte Identification and More
Accurate Quantitation W. Christopher Siegler; James Griffith; Bill Winniford; Kefu Sun; Jim Luong; Rob
Edam; Patric Eckerle
The Dow Chemical Company, Freeport, TX USA
P-147-M
Position Specific Isotopic Analysis using a Hybrid GCxPyrolysis-GC Coupled to
Combustion Isotope Ratio Mass Spectrometry Herbert Tobias; J. Thomas Brenna
Cornell University, Ithaca, NY USA
P-148-M
High Sensitivity Flow-modulated Two-dimensional Gas Chromatography-Mass
Spectrometry Flavio Franchina
1; Mariosimone Zoccali
1; Peter Tranchida
1; Luigi Mondello
1, 2
1SCIFAR, University of Messina, Messina, Italy;
2C.I.R., University Campus-Biomedico,
Rome, Italy
50
P-149-M
Applications of GC×GC-High Resolution TOFMS Coupled with the Classical Soft
Ionization Technique “Field Ionization” Masaaki Ubukata
1; John Dane
1; Robert B. Cody
1; Jun Onodera
2; Keisuke Ishii
2; Zhanpin
Wu3
1JEOL USA, Inc., Peabody, MA USA;
2JEOL Ltd., Tokyo, Japan;
3Zoex Corporation,
Houston, TX USA
P-150-M
MetPP: A Computational Platform for Comprehensive Two-Dimensional Gas
Chromatography Time-of-Flight Mass Spectrometry-Based Metabolomics Xiang Zhang
University of Louisville, Louisville, KY USA
51
Micellaneous Applications of GC×GC
P-112-M
Determination of the Unsaponifiable Fraction of Milk Lipids using GC×GC-
MS/FID Supported by HR ToF MS for Structural Confirmation Simona Salivo
1; Peter Tranchida
1; Carla Ragonese
1; Marco Beccaria
1; Luigi Mondello
1, 2
1SCIFAR, University of Messina, Messina, Italy;
2C.I.R., University Campus-Biomedico,
Rome, Italy
P-124-M
Qualitative and Quantitative Chemical Characterization of Volatile Organic
Compunds in Indoor Air Environment by Different Chromtographic Techniques:
GC×GC-TOFMS, GC-MS, GC-FID Joseane Ames
1; Alessandro Casilli
1; Adriana Gioda
2; Débora Almeida Azevedo
1
1Universidade Federal do Rio de Janeiro, Rio De Janeiro, Brazil;
2Pontifícia
Universidade Católica do Rio de Janeiro, Rio de Janeiro, Brazil
52
ISCC 2013
Scientific Program Summary
Tuesday, May 14, 2013
08:00 – 17:20 Registration in the Ballroom Foyer
08:30 – 08:45 ISCC Introduction and Welcome
Frantisek Svec, Lawrence Berkeley National Laboratories,
Berkeley, CA USA
Golay Award Plenary Lecture in Catalina and Madera Ballrooms Session Chairs: Milos Novotny, Indiana University, Bloomington, IN USA
and Andrew Tipler, PerkinElmer, Shelton, CT USA
08:45 – 09:30 (L-02-01)
From Packed LC-columns via SFC to Open Tubular LC-
columns
Tyge Greibrokk, University of Oslo, Oslo, Norway
Plenary Lecture in Catalina and Madera Ballrooms Session Chair: James Jorgenson, University of North Carolina, Chapel Hill, NC USA
09:30 – 10:00 (L-02-02)
Comprehensive 2D Chromatography: A Key to Unlock Closed
Analytical Doors
Luigi Mondello, SCIFAR, University of Messina, Messina, Italy
10:00 – 10:30 AM Break – Visit the Exhibitors and Posters in the Foyer and
Pasadena, Sierra and Ventura Ballrooms
10:30 – 11:00 (L-02-03)
Ionic Liquids in GC for Water Analysis and for LC-MS of
Trace Anions
Dan Armstrong, University of Texas at Arlington, Arlington, TX
USA
11:00 – 11:30 (L-02-04)
Ordered Monolithic Structures as Stationary Phases for
Capillary Chromatography
Emily Hilder; Dario Arrua; Paul Haddad; Katharina Dihm,
ACROSS, University of Tasmania, Hobart, Australia
53
Tuesday, May 14, 2013 continued…
11:30 – 12:00 (L-02-05)
Transport of Single DNA Molecules through Nanofluidic
Channels Laurent Menard; Jinsheng Zhou; J. Michael Ramsey, University of
North Carolina, Chapel Hill, NC USA
12:00 – 13:00 Technical Seminars
Addressing Analytical Challenges Using High Performance Gas Chromatography
and Two-Dimensional Gas Chromatography
Jef Focant, University of Liége, Liége, Belgium
Sponsored by LECO Corporation Mojave Learning Center
Twice the Column, Better Separations, Same Analysis Time: Analysis of the EFSA
PAH4 with the New Rxi-PAH GC Column
Half the Column, Same Separation: Extending the Lifetime of a GC Column after
Column Trimming Maintenance with Method Translation
Jack Cochran, Amanda Rigdon, Roy Lautamo, Shawn Reese, Michelle Misselwitz;
Restek Corporation, Bellefonte, PA USA
Sponsored by Restek Corporation Catalina Ballroom
Part 1: Advancements In Modern Chromatography Equipment Design To Do More
With Less
Terri Christison1; Massimo Santoro
2,
1Thermo Scientific, Sunnyvale, CA USA;
2Thermo
Scientific, Lombardy, Italy
Part 2: Capillary Ion Chromatography – Always On, Always Ready
Terri Christison1; Massimo Santoro
2,
1Thermo Scientific, Sunnyvale, CA USA;
2Thermo
Scientific, Lombardy, Italy
Sponsored by Thermo Scientific Madera Ballroom
13:00 – 14:00 Lunch – Participants on their own
14:00 – 15:30 Poster Session – Visit the Exhibitors and Posters in the Foyer and
Pasadena, Sierra and Ventura Ballrooms
54
Tuesday, May 14, 2013 continued…
Microfluidics Session in the Mojave Learning Center
Session Chairs: Will Black, University of North Carolina, Chapel Hill, NC USA
and Susanne Wiedmer, University of Helsinki, Helsinki, Finland
15:30 – 15:55 (L-02-11)
Automation of Cell Synchronization and Analysis on
Microfluidic Devices
Stephen Jacobson; Seth Madren; Michelle Hoffman; Pamela
Brown; David Kysela; Yves Brun, Indiana University,
Bloomington, IN USA
15:55 – 16:20 (L-02-12)
Size-Selective Protein Fractionation in Arrays of Nanofluidic
Channels
Adam Woolley; Suresh Kumar; Jie Xuan; Aaron Hawkins; Milton
Lee; Brigham Young University, Provo, UT USA
16:20 – 16:40 (L-02-13)
Dielectrophoresis Applied to Biomolecule Manipulation and
Nanocrystal Sorting Alexandra Ros, Arizona State University, Tempe, AZ USA
16:40 – 17:00 (L-02-14)
Microchip Based Methods for Monitoring Nitric Oxide
Metabolites in Single Cells and Freely Roaming Animals Susan Lunte, University of Kansas, Lawrence, KS USA
17:00 – 17:20 (L-02-15)
Integrated Microfluidic Devices for Monitoring Nitric Oxide
Production in Single Cells
Eve C. Metto; Dulan B. Gunasekara; Susan M. Lunte; Christopher
T. Culbertson, Kansas State University, Manhattan, KS USA
17:30 – 19:00 Exhibitor Reception – Visit the Exhibitors in the Ballroom Foyer
55
Wednesday, May 15, 2013
07:30 – 08:30 Meet the Expert – Students and Postdoc Only in the Ballroom
Courtyard
08:00 – 18:00 Registration in the Ballroom Foyer
Instrumentation Development in the Catalina and Madera Ballrooms
Session Chair: Mark Libardoni, Southwest Research Institute, San Antonio, TX USA
and Jim Luong, Dow Chemical Canada, Fort Saskatchewan, AB Canada
08:30 – 08:55 (L-03-01)
Ultra-fast, High Mass-resolution Multi-Reflection-Time-of-
Flight-Mass Spectrometer as Detector for One-dimensional
and Comprehensive Two-Dimensional Gas Chromatography:
Characterization of Highly Complex Mixtures Ralf Zimmermann
1; Thomas Gröger
1; Marie Schäffer
1; Benedikt
Weggler1; Jürgen Wendt
2; Martin Sklorz
1; Theo Schwemer
1,
1University of Rostock/Helmholtz Zentrum München, Munich,
Germany, 2LECO Instrumente GmbH, Mönchengladbach,
Germany
08:55 – 09:20 (L-03-02)
GC×GC with a Low-Power, Low-Resource, Microfabricated
Thermal Modulator
Gustavo Serrano; Dibyadeep Paul; Will Collin; Amy Bondy;
Katsuo Kurabayashi; Edward Zellers, University of Michigan, Ann
Arbor, MI USA
09:20 – 09:40 (L-03-03)
Tandem Differential Mobility Spectrometer: An Ionization
Detector for Gas Chromatography with High Speed, Selective,
Small Size and Low Cost
G.A. Eiceman; M. Menlyadiev, New Mexico State University, Las
Cruces, NM USA
56
Wednesday, May 15, 2013 Continued…
09:40 – 10:00 (L-03-04)
Screening for Chlorinated Dioxins and Furans in Soil and
Sediment Using Bio-Assay and GC×GC-TOFMS, with
Confirmation by GC-HRT and GC×GC-HRT
Peter Gorst-Allman1; Jayne de Vos
2; Laura Quinn
2; Claudine
Roos3; Rialet Pieters
3; Egmont Rohwer
4; John Giesy
5,6,7,8; Henk
Bouwman3,
1LECO Africa (Pty) Ltd, Kempton Park, South Africa;
2National Metrology Insitute of South Africa, Pretoria, South
Africa; 3North West University, Potchefstroom, South Africa;
4University of Pretoria, Pretoria, South Africa;
5University of
Saskatchewan, Saskatoon, SK Canada; 6Michigan State
University, East Lansing, MI, USA; 7King Saud University,
Riyadh, Saudi Arabia; 8City University of Hong Kong, Kowloon,
Hong Kong, China
10:00 – 10:30 AM Break – Visit the Exhibitors and Posters in the Foyer and
Pasadena, Sierra and Ventura Ballroom
Column Technologies I in the Mojave Learning Center
Session Chairs: Gert Desmet, Vrije Universitiet Brussel, Brussels Belgium
and Fernando Maya Alejandro, Universitat de les Illes Balears, Palma de Mallorca, Spain
08:30 – 08:55 (L-03-05)
New Macroporous UHPLC Silica Particles for Biomolecular
Separations
Milos V. Novotny, Benjamin F. Mann, Amanda K.P. Mann, Sara
E. Skrabalak, Indiana University, Bloomington, IN USA
08:55 – 09:20 (L-03-06)
New Polymeric Monoliths with Structure Optimized for
Molecular Mass Separation of Polymers Alexander Kurganov; Anastasiya Kanatyeva, Institute of
Petrochemical Synthesis, Moscow Russia
09:20 – 09:40 (L-03-07)
Generating More than 100,000 Theoretical Plates with Less
than 50 Bar in Liquid Chromatography with Porous Pillar
Arrays Manly Callewaert
1; Jeff Op De Beeck
1; Heidi Ottevaere
1; Han
Gardeniers2; Gert Desmet
1; Wim De Malsche
1,
1Vrije Universiteit
Brussel, Brussels Belgium; 2Mesa+ Institute of Nanotechnology,
Enschede The Netherlands
57
Wednesday, May 15, 2013 continued…
09:40 – 10:00 (L-03-08)
Preconcentration of Aromatic Compounds in Aqueous
Samples with Polymer-Coated Fiber-Packed Capillary and the
Subsequent Temperature-Programmed Elution with Water Yuuhi Mori
1; Kenichi Nakane
1; Akira Kobayashi
1; Ikuo Ueta
2;
Hayato Takeuchi1; Kiyokatsu Jinno
1; Yoshihiro Saito
1;
1Toyohashi
University of Technology, Toyohashi, Japan; 2University of
Yamanashi, Kofu, Japan
10:00 – 10:30 AM Break – Visit the Exhibitors and Posters in the Foyer and
Pasadena, Sierra and Ventura Ballrooms
Applications of Gas Chromatography in the Catalina and Madera Ballrooms Session Chair: Kevin Thurbide, University of Calgary, Calgary, AB Canada
10:30 – 10:55 (L-03-09)
Identification of Unknown Metabolites with Accurate Mass
GC-Chemical Ionization QTOF Mass Spectrometry Oliver Fiehn; John Meissen; Takeuchi Kouhei; Sean Adams
University of California, Davis, Davis, CA USA
10:55 – 11:20 (L-03-10)
GC and GCMS for Solar System Geochemistry and Planetary
Atmospheres – Past Missions to State-of-the-Art Instrument
Development
Mark Libardoni, Southwest Research Institute, San Antonio, TX
USA
11:20 – 11:40 (L-03-11)
Multidimensional GC Combined with Accurate Mass, Tandem
Mass Spectrometry, and Element-specific Detection for
Identification of Sulfur Compounds in Tobacco Smoke Nobuo Ochiai
1; Kikuo Sasamoto
1; Kazuhisa Mitsui
2; Yuta
Yoshimura2; Frank David
3; Pat Sandara
3,
1GERSTEL KK, Tokyo
Japan; 2Japan Tobacco Inc., Kanagawa Japan;
3Research Institute
of Chromatography, Kortrijk Belgium
58
Wednesday, May 15, 2013 continued…
11:40 – 12:00 (L-03-12)
Multidimensional Gas Chromatography and Planar
Microfluidics with Tandem Sulfur Chemiluminescence and
Flame Ionization Detection for Sulfur Compounds Analysis
Jim Luong1; Ronda Gras
1; Robert Shellie
2; Hernan Cortes
2,3,
1Dow
Chemical Canada, Fort Saskatchewan, AB Canada; 2ACROSS,
University of Tasmania, Hobart, Australia; 3HJCortes Consulting
LLC, Midland, TX USA
Electrodriven Methods in the Mojave Learning Center
Session Chair: Christopher Palmer, University of Montana, Missoula, MT USA
10:30 – 10:55 (L-03-13)
Combination of On-Line Sample Concentration and Mass
Spectrometric Detection in Microscale Electrophoresis Hiroshi Koino
1; Hiroya Ota
1; Mami Oketani
1; Takayuki Kawai
2;
Kenji Sueyoshi1; Takuya Kubo
1; Fumihiko Kitagawa
3; Koji
Otsuka1,
1Kyoto University, Kyoto Japan;
2National Institute of
Advanced Industrial Science, Ikeda Japan; 3Hirosaki University,
Hirosaki, Japan
10:55 – 11:20 (L-03-14)
Separation of Carbon Dots by Capillary Electrophoresis Luis Colon; John Vinci; Ivonne Ferrer; Zuqin Xue, University at
Buffalo, Buffalo, NY USA
11:20 – 11:40 (L-03-15)
Characterization of Phosphonium-based Ionic Liquids and
Their Use in Electrokinetic Capillary Chromatography Susanne Wiedmer
1; Annika Railila
1; Jana Lokajová
2; Ashley
Holding1; Alistair King
1,
1University of Helsinki, Helsinki
Finland; 2Institute of Organic Chemistry and Biochemistry,
Prague Czech Republic
11:40 – 12:00 (L-03-16)
Capillary Electrophoresis in Classical and Carrier
Ampholytes-Based Background Electrolytes Applied to
Separation and Physicochemical Characterization of Peptide
Hormones
Vaclav Kasicka1; Veronika Solinova
1; Dusan Koval
1; Martine
Poitevin2; Jean-Marc Busnel
2; Gabriel Peltre
2,
1Czech Academy of
Science, Prague, Czech Republic; 2Ecole Super De Physique et
Chimie Industrielles, Paris, France
59
Wednesday, May 15, 2013 continued…
12:00 – 13:00 Technical Seminars
TBD
Sponsored by
Supelco, A Member of the SIGMA-ALDRICH Group Mojave Learning Center
TBD
Sponsored by Zoex Corporation Catalina Ballroom
13:00 – 14:00 Lunch – Participants on their own
14:00 – 15:30 Poster Session – Visit the Exhibitors and Posters in the Foyer and
Pasadena, Sierra and Ventura Ballroom
Young Scientist - GC in the Catalina and Madera Ballrooms Session Chair: Robert E. Synovec, University of Washington, Seattle, WA USA
15:30 – 15:45 (L-03-17)
Better Sniffing – A Story of High-Resolution Wine Aroma
Analysis
Sung-Tong Chin1; Graham Eyres
2; Philip Marriott
1,
1Monash
University, Clayton, Australia; 2CSIRO Animal, Food and Health
Sciences, Sydney, Australia
15:45 – 16:00 (L-03-18)
User-friendly Method for GC×GC Optimization Pierre-Hugues Stefanuto; Jean-Marie Dimandja; Jean-François
Focant, University of Liège, Liège Belgium; Spelman College,
Atlanta, GA USA
16:00 – 16:15 (L-03-19)
Efficiency of Monolithic Capillary Columns in High Pressure
Gas Chromatography Anastasiya Kanatyeva; Alexander Kurganov; Alexander Korolev;
Valeriya Shiryaeva; Tamara Popova, TIPS RAS, Moscow Russia
16:15 – 16:30 (L-03-20)
Evaluation of First Responders’ Exposure to Mixed Halogen
Planar Compounds in Fire Debris Using Comprehensive Two
Dimensional Gas Chromatography Kari Organtini
1; Frank Dorman
1; Mark Merrick
2,
1The
Pennsylvania State University, University Park, PA USA; 2LECO
Corporation, St. Joseph, MI USA
60
Wednesday, May 15, 2013 continued…
16:30 – 16:45 (L-03-21)
From the Olympics to the North Sea Gas Fields –Using
GC×GC to Investigate Atmospheric Complexity
Richard Lidster; Jacqueline Hamilton; Alastair Lewis; Rachel
Holmes; James Lee; James Hopkins, The University of York, York,
United Kingdom
Young Scientist - LC in the Mojave Learning Center Session Chairs: Milton Lee, Brigham Young University, Provo, UT USA
and Mary Wirth, Purdue University, West Lafayette, IN USA
15:30 – 15:45 (L-03-23)
Development of a 2D LC-CE-ESI Platform for Peptide
Mapping Applications
Will Black; J. Scott Mellors; J. Michael Ramsey, University of
North Carolina, Chapel Hill, NC USA
15:45 – 16:00 (L-03-24)
Packing and Characterization of High Aspect Ratio LC
Columns in Capillaries and Microfluidic Devices
James Grinias1; Martin Gilar
2; James Jorgenson
1,
1University of
North Carolina, Chapel Hill, NC USA; 2Waters Corporation,
Milford, MA USA
16:00 – 16:15 (L-03-25)
Porous Monolithic Thin Layers for TLC-MS Separations Alexandros Lamprou; Zhixing Lin; Yongqin Lu; Frantisek Svec,
Lawrence Berkeley National Laboratory, Berkeley, CA USA
16:15 – 16:30 (L-03-26)
“Knitting” Poly(Styrene-divinylbenzene) Capillary Monoliths
with Large Surface Area via Friedel-Crafts Alkylation with
External Crosslinkers Fernando Maya Alejandro
1; Frantisek Svec
2; Victor Cerdá
1,
1Universitat de les Illes Balears, Palma de Mallorca Spain;
2Lawrence Berkeley National Laboratory, Berkeley, CA USA
16:30 – 16:45 (L-03-27)
Development of a Capillary Column Coated with C60-Fullerene
for Liquid Chromatographic Separations Yoshiki Murakami; Takuya Kubo; Koji Otsuka
Kyoto University, Kyoto, Japan
61
Wednesday, May 15, 2013 continued…
17:00 – 18:00 Panel Discussions
Prospects of Microfluidics in Chemical Separations
Moderator:
J. Michael Ramsey, University of North Carolina, NC USA
Panel:
Stephen Jacobson, Indiana University, Bloomington, IN USA
Alexandra Ros, Arizona State University, Tempe, AZ USA
Adam Woolley, Brigham Young University, Provo, UT USA
Catalina and Madera Ballrooms
62
Thursday May 16, 2013
07:30 – 08:30 Meet the Expert – Students and Postdocs Only in the Ballroom
Courtyard
08:00 – 16:30 Registration in the Ballroom Foyer
Gas Chromatography Technology in the Catalina and Madera Ballrooms Session Chair: Joshua Whiting, 3 Degrees of Separation, Inc., Dayton, OH USA
08:30 – 08:55 (L-04-01)
Development of a New Capillary Column Format Utilizing
Single Column and Parallel Column Array Geometries for
Improved Separations
Frank Dorman, Penn State University, University Park, PA USA
08:55 – 09:20 (L-04-02)
Germania-Based Sol-Gel Materials in Separation Science Abdul Malik; Chengliang Jiang; Abdullah Alhendal; MinhPhuong
Tran; Emre Seyyal, University of South Florida, Tampa, FL USA
09:20 – 09:40 (L-04-03)
Practical Reduction of Analysis Time in GC and GC/MS Using
Existing Instrumentation
Jaap De Zeeuw; Jim Whitford, Restek Corporation, Middelburg,
The Netherlands
09:40 – 10:00 (L-04-04)
New Developments in Ionic Liquid GC Stationary Phases
Leonard M. Sidisky; James L. Desorcie; Greg A. Baney; Gustavo
Serrano; Daniel L. Shollenberger; Katherine K. Stenerson,
Supelco, A Member of the SIGMA-ALDRICH Group, Bellefonte,
PA USA
10:00 – 10:30 AM Break - Visit the Exhibitors and Posters in the Foyer and
Pasadena, Sierra and Ventura Ballrooms
Column Technologies II in the Mojave Learning Center
Session Chair: James Grinias, University of North Carolina, Chapel Hill, NC USA
and John C. Vinci, University at Buffalo, Buffalo, NY USA
08:30 – 08:55 (L-04-05)
Improving Efficiency in Monolithic Capillary Column Liquid
Chromatography Pankaj Aggarwal; Kun Liu; Dennis Tolley; John Lawson; Milton
Lee, Brigham Young University, Provo, UT USA
63
Thursday May 16, 2013 continued…
08:55 – 09:20 (L-04-06)
Recent Advances in Pillar Array Column Technology Gert Desmet; Jeff Op De Beeck; Manly Callewaert; J.G.E.
Gardeniers; Wim DeMalsche, Vrije Universitiet Brussel, Brussels
Belgium
09:20 – 09:40 (L-04-07)
Nanoparticle-Based Sample Preparation for Biomarker
Analysis by HPLC-MS/MS
Michael Lämmerhofer1; Helmut Hinterwirth
2; Elisabeth Haller
2;
Wolfgang Lindner2,
1University of Tuebingen, Tuebingen,
Germany; 2University of Vienna, Vienna, Austria
10:00 – 10:30 AM Break - Visit the Exhibitors and Posters in the Foyer and
Pasadena, Sierra and Ventura Ballroom
Sampling/Chemistry in the Catalina and Madera Ballrooms Session Chair: G.A. Eiceman, New Mexico State University, Las Cruces, NM USA
10:30 – 10:55 (L-04-09)
Particulate Matter Composition as a Measure of Residential
Wood Stove Emissions: Analytical Methods and
Measurements in Impacted Air Sheds Christopher Palmer; Brittany Busby; Megan Bergauf; Tony Ward,
University of Montana, Missoula, MT USA
10:55 – 11:20 (L-04-10)
The Discovery of Attribution Signatures for Chemical Threat
Agents Carlos Fraga, Pacific Northwest National Laboratory, Richland,
WA USA
11:20 – 11:40 (L-04-11)
Chemical and Botanical Diversity Studied through
Chromatographic Analysis of Tropical Plants Secondary
Metabolites Elena Stashenko, Industrial University of Santander,
Bucaramanga, Colombia
11:40 – 12:00 (L-04-12)
Sulfur Response Characteristics of a Novel Multi-Flame
Photometric Detector for GC Kevin Thurbide; Adrian Clark, University of Calgary, Calgary, AB
Canada
64
Thursday May, 16, 2013 continued…
12:00 – 13:30 Lunch Break – Participants on their own
LC×LC in the Mojave Learning Center Session Chairs:
Vaclav Kasicka, Academy of Sciences of the Czech Republic, Prague Czech Republic
and Luigi Mondello, SCIFAR, University of Messina, Messina Italy
10:30 – 10:55 (L-04-13)
Method Development of Two-dimension Liquid
Chromatography and its Practicability in Separating Complex
Samples Qin Yang; Xianzhe Shi; Shuangyuan Wang; Lizhen Qiao;
Yuanhong Shan; Xin Lu; Guowang Xu, Dalian Institute of
Chemical Physics, CAS, Dalian China
10:55 – 11:20 (L-04-14)
High Peak Capacity Separations of Biologically-important
Molecules by using 2D LC×UHPLC
Paola Donato, Università Campus Bio-Medico, Rome Italy
11:20 – 11:40 (L-04-15)
On-line Coupling of Size Exclusion Chromatography with
Mixed-mode Liquid Chromatography for Comprehensive
Profiling of Biopharmaceutical Drug Product Yan He; Olga Friese; Qian Wang; Laura Bass; Michael Jones,
Pfizer, Inc. Chesterfield, MO USA
12:00 – 13:30 Lunch Break – Participants on their own
Microfab GC and GC×GC in the Catalina and Madera Ballrooms Session Chair: Carlos Fraga, PACIFIC NORTHWEST NATIONAL LABORATORY,
Richland, WA USA
13:30 – 13:50 (L-04-17)
A Portable Microfabricated GC×GC for Vapor Sampling and
Analysis R.J. Simonson
1; D.H. Read
1; A.W. Staton
1; J.J. Whiting
2,
1Sandia
National Laboratory, Albuquerque, NM USA; 2Three Degrees of
Separation, Inc., Dayton, OH USA
13:50 – 14:10 (L-04-18)
Advances in Micro and Nano-Fabricated Silicon Devices for
Gas Chromatography Joshua Whiting, 3 Degrees of Separation Inc., Dayton, OH USA
65
Thursday May, 16, 2013 continued…
14:10 – 14:30 (L-04-19)
A Micro Discharge Device as a Low Power Universal Multi-
Channel Detector for Portable and MEMS Gas
Chromatographs
Adam McBrady, Honeywell ACS, Plymouth, MN USA
14:30 – 14:45 Mini Break
Applications Liquid Chromatography in the Mojave Learning Center Session Chairs:
Alexandros Lamprou, Lawrence Berkeley National Laboratory, Berkeley, CA USA
and Guowang Xu, Dalian Institute of Chemical Physics, Dalian, China
13:30 – 13:50 (L-04-20)
Microfluidic Western Blot Robert Kennedy, University of Michigan, Ann Arbor, MI USA
13:50 – 14:10 (L-04-21)
Rapid Isolation of High Solute Amounts by Using an On-Line
4D Chromatographic System (Prep LC-GC-GC-GC) Danilo Sciarrone
1; Sebastiano Panto
1; Peter Quinto Tranchida
1;
Paola Dugo1,2
; Luigi Mondello1,2
, 1SCIFAR, University of Messina,
Messina Italy; 2University Campus Bio-Medico of Rome, Rome,
Italy
14:10 – 14:30 (L-04-22)
Tagging Strategies for Capillary LC-MS Carbonyl
Metabolomics James Edwards, Saint Louis University, St. Louis, MO USA
14:30 – 14:45 Mini Break
Plenary Lecture in the Catalina and Madera Ballrooms
Session Chair: Emily Hilder, ACROSS, University of Tasmania, Hobart, Australia
14:45 – 15:15 (L-04-23)
Ultrahigh Performance Capillary LC Using Submicrometer
Silica Particles
Mary Wirth, Purdue University, West Lafayette, IN USA
66
Thursday May, 16, 2013 continued…
15:15 – 15:45 (L-04-24)
Packing Capillary LC Columns with Sub-2 Micron Particles:
Everything I Know is Wrong
James Jorgenson; Edward Franklin; Laura Blue; James Grinias,
University of North Carolina, Chapel Hill, NC USA
15:45 – 16:15 (L-04-25)
Capillary Electrophoresis for Deep and Accurate Bottom-Up
Proteomics
Norm Dovichi, University of Notre Dame, Notre Dame, IN USA
16:15 – 16:30 Announcements of Awards and Posters
16:30 – 16:40 Invitation to 2014
Luigi Mondello, SCIFAR, University of Messina, Messina, Italy
16:40 – 16:45 Closing Comments
Robert E. Synovec, University of Washington, Seattle, WA USA
67
L-02-01
From Packed LC-columns via SFC to Open Tubular LC-columns
Tyge Greibrokk
University of Oslo, Oslo, Norway
Throughout his career this author has aimed at developing the tools for analyzing small
samples containing small amounts of analytes that has a tendency to disappear on large
chromatography columns, and to do this with maximum selectivity and sensitivity.
Starting with searching for peptide hormones in the hypothalamus of the brain, as post
doc at the University of Texas at Austin, the basis for a life in chromatographic research
was established. The pioneering work on HPLC of peptides in Austin was continued
coming back to the University of Oslo, where a research group in analytical
chemistry/chromatography was established and students were recruited. After some years
in the development of HPLC-methods, another chromatographic technique had come to
the eyes of the chromatographers in the US, particularly at Hewlett Packard; supercritical
fluid chromatography. In the first part of the 80s the equipment for SFC consisted of
upgraded HPLC instrumentation. By installing extra check valves and cooling on valves
and pump heads on Waters 6000 pumps, we obtained a reliable mobile phase delivery
unit combining CO2 and modifiers for pressure gradients, temperature gradients and
combinations of both. By examining the properties of open tubular columns the detection
capabilities was extended from UV to FID and MS. Large volume injection on OT-SFC
became an important issue and by solvent venting techniques several microliters could be
injected on 50µm i.d. columns. The combination of SFC and MS had become common,
but for environmental applications there was a lack of selectivity for halogenated
compounds. Thus, we developed a microplasma GC-MS detector able of determining
selectively halogenated compounds at high sensitivity of each halogen. This became our
only contribution to gas chromatography.
In the end, plain CO2 did not provide the solubilities needed for many applications and
our attention again became focused on modified CO2 on packed columns, but now mainly
with 1 mm i.d. columns. Supported by the petroleum- and the polymer industry, group
separation on coupled columns and separation of oligomers of polymer additives were
obtained mainly with light scattering detection with special made nebulizers for narrow
bore columns. Both pressure and temperature were used as variables.
Based on our experience with narrow bore columns in SFC, we decided to use such
columns in HPLC where a broader selection of both mobile phases and stationary phases
are available. From our experience with SFC we realized that the active use of
temperature could be transferred to HPLC, as long as we maintained the narrow bores.
Thus we packed 0.32 mm i.d. columns, even established a small company producing high
quality columns, which could be used for not only solvent gradients, but also for
temperature gradients. The 1 mm i.d. columns that were commercially available at this
time did not withstand temperature gradients. For the improvement of selectivity and less
68
ionization suppression in MS, two-dimensional systems were developed. Lowered
temperature and even chromatofocusing techniques were developed for sample
reconcentration at the column inlet. Thus, the use of packed capillary columns was the
trade mark of the Oslo group for several years, until we decided to venture into open
tubular columns for LC. The background was the wish to reduce band broadening in the
column even further. Unfortunately, several groups had worked with OT-LC since the
end of the 70s, without much success. However, a brake-through came in 2006-7 with the
porous layer (PLOT) columns from the Svec and Karger groups. Following their
developments we have made many 5-10 µm i.d. PLOT columns with 0.5-1 µm
monolithic layers and have concluded that such columns are fairly easy to make
reproducibly. The columns have been included in proteomics applications, both for intact
proteins and for peptides. Two-dimensional coupled systems have been developed, with
different stationary phases, also short monolithic columns and including columns for
enzymatic degradation of proteins. Thus, starting with 2-3 m long 2.6 mm i.d. columns
packed with 37-54 µm particles for peptides 40 years ago, we are now working with 2-8
m long 10 µm i.d. open tubular columns for proteins, peptides and even smaller
molecules. The improvements in column technology in this period have been
tremendous, but for this author the circle also appears to have been closed.
Notes:
69
L-02-02
Comprehensive 2D Chromatography: A Key to Unlock Closed Analytical Doors
Luigi Mondello1, 2
1SCIFAR, University of Messina, Messina, Italy;
2C.I.R., University Campus Bio-Medico
of Rome, Rome, Italy
Comprehensive chromatography (CC) experiments are usually carried out on two
analytical columns, linked in series, and with an independent (orthogonal) selectivity. A
transfer device (generically defined as modulator), positioned (somewhere) between the
two dimensions, enables the isolation and re-injection of chromatography bands from the
first to the second column, in a sequential manner throughout the analysis. Separations in
the second dimension are usually carried out in a rapid manner, and ideally must end
before the next re-injection step. Consequently, a CC analysis can be considered as
nothing more than a stream of fast one-dimensional analyses, performed on the secondary
column. The most appraised advantage of CC methods, over the one-dimensional
counterparts, is the enhanced resolving power: in theory, the peak capacity (nc) becomes
that of the primary column, multiplied by that of the second. The present oral
contribution is focused on the analytical benefits of CC methods (i.e., 2D GC, 2D LC,
etc.), which have been exploited and emphasized by a constantly increasing part of the
chromatography community, in particular over the last twenty years. The power of CC
methods, along with recent advances in mass spectrometry (MS), have enabled a much
deeper insight into the true qualitative and quantitative composition of real-world
samples. In fact, the unsuspected complex nature of a multitude of sample-types has been
elucidated through the enhanced resolving power of such analytical approaches.
Additionally, the outstanding selectivity and sensitivity of specific CC methodologies (in
particular with MS detection) has made trace (ppb level), and ultra-trace (ppt level and
lower) target analysis feasible, reducing the need for tedious sample preparation
processes.
Notes:
70
L-02-03
Ionic Liquids in GC for Water Analysis and for LC-MS of Trace Anions
Daniel W. Armstrong
University of Texas at Arlington, Arlington, TX USA
The excellent stability of ionic liquids (ILs) to temperature, water and oxygen make them
exceptional stationary phases for extreme conditions and/or direct analysis of “harsh-
matrix” samples. By synthesizing ILs of specific architectures, good peak shapes and
reasonable retentions for analytes like water can be obtained. Also it will be
demonstrated that the amount of water in solids (including pharmaceutical products) can
be easily accomplished using a specific IL – head space technique. Finally, recent results
on the ultra- trace analysis of anionic pesticides and performance enhancing drugs by LC-
MS, using specifically engineered IL cations, will be discussed.
Notes:
71
L-02-04
Ordered Monolithic Structures as Stationary Phases for Capillary Chromatography
Emily Hilder; Dario Arrua; Paul Haddad; Katharina Dihm
ACROSS, University of Tasmania, Hobart, Australia
Polymer based monoliths were introduced about 20 years ago as a new generation of
stationary phases in separation science with recognised advantages over traditional
particle packed columns. To date the majority of monolithic structures explored for
analytical applications have been based on the same synthetic approach first described by
Svec and Fréchet [1]. However, as new chromatographic systems challenge the
theoretical limits of high performance chromatography, it is now clear that one of the
limiting factors in preparing reproducible polymer monoliths with good chromatographic
performance is the degree of bed heterogeneity. Novel polymerisation methods are
needed to improve the structural homogeneity, reducing the contribution of eddy
dispersion to band broadening and allowing polymer monoliths to reach their true
potential for analytical applications. This presentation will introduce a range of
approaches that we have explored to improve both the separation efficiency and
selectivity of separations of both small and large molecules using polymer monoliths for
capillary liquid chromatography. These include new synthetic approaches such as
incorporation of nanoparticles into the monolithic structure or synthesis using
cryopolymerisation approaches (with and without unidirectional freezing) [2], as well as
approaches to extend the operating conditions for these column types, particularly
through the use of very high temperature gradients or rapid pulses. Examples will be
provided where the performance of polymeric monolithic columns is shown to be
superior to packed particle columns.
Notes:
72
L-02-05
Transport of Single DNA Molecules through Nanofluidic Channels
Laurent Menard; Jinsheng Zhou; J. Michael Ramsey
University of North Carolina, Chapel Hill, NC USA
Nanofluidic platforms have been established as valuable tools for single molecule studies
of macromolecules. In particular, significant effort has been invested in the development
of fabricated nanochannels and nanopores for single molecule analyses of DNA. This
work has advanced the fundamental understanding of polymer behavior under
confinement and promises to offer technological value in applications such as DNA
sizing, mapping, epigenetic analysis, and sequencing. All of these applications rely on
the ability to extend relatively large DNA molecules (>1000 bases) from the random coil
observed in free solution into linearized conformations suitable for spatially resolved
characterizations. Confinement of DNA molecules in nanochannels having critical
dimensions (width and depth) less than ~100 nm is an effective method for achieving this
spatial control. As the nanochannel dimensions decrease, the conformational degrees of
freedom available to a confined DNA molecule are reduced, and linear extension and
longitudinal spatial resolution increase. Fabricating nanochannels with critical
dimensions below 30 nm remains a significant technological challenge. The simplest
devices consist of single nanochannels or arrays of parallel nanochannels. These devices
were used to study the dynamics of electrokinetically-driven transport of single DNA
molecules through nanochannels. The DNA molecules were stained with an intercalating
dye (YOYO-1, Invitrogen) and observed on an inverted fluorescence microscopy (Nikon
TE-2000) using a 60X or 100X oil immersion objective lens. Images were recorded at
350-400 frames/s using an electron-multiplying CCD camera (Photometrics Cascade II).
From images such as these, the mobility of DNA molecules under varying degrees of
confinement and important intramolecular relaxation dynamics were determined. DNA
transport in channels as small as 20 nm has been characterized.
Notes:
73
L-02-11
Automation of Cell Synchronization and Analysis on Microfluidic Devices
Stephen Jacobson; Seth Madren; Michelle Hoffman; Pamela Brown; David Kysela; Yves
Brun
Indiana University, Bloomington, IN USA
A detailed understanding of the mechanisms by which bacteria adhere to surfaces is
essential to elucidate how biofilms form and bacteria infect. The ability to track these
adhesion events at the single cell level with fluorescence microscopy provides insight
into the adhesion process and heterogeneity of the process within a given cell population.
With microfluidic devices, we are able to precisely control the local environment in
which the cells reside and to monitor the behavior of the bacterium Caulobacter
crescentus. To improve temporal precision, we moved the cell synchronization step on
chip and developed a microfluidic “baby machine.” The microfluidic devices have
integrated pumps and valves to control the movement of cells and media. Synchronized
populations are collected from the device at intervals as short as 10 min and at any time
over four days. Our on-chip synchronization method overcomes limitations with
conventional physical cell separation methods that consume large volumes of media,
require manual manipulations, have lengthy incubation times, are limited to one
collection, and lack precise temporal control of collection times. We now have a closed,
automated system that streamlines the steps of cell seeding, culture, synchronization, and
analysis.
Notes:
74
L-02-12
Size-Selective Protein Fractionation in Arrays of Nanofluidic Channels
Adam Woolley; Suresh Kumar; Jie Xuan; Aaron Hawkins; Milton Lee
Brigham Young University, Provo, UT USA
Methods for the size-selective fractionation of particles and molecules with dimensions in
the tens of nanometers have limitations. Although gel electrophoresis and size-exclusion
chromatography offer separation capabilities in this size range, denaturing conditions are
often needed for proteins in gel electrophoresis, and size-exclusion chromatography has
rather limited resolution. We have thus been exploring alternative approaches for size-
based analysis of biomolecules. We have demonstrated a process for making nanofluidic
channel arrays using thin-film microfabrication technology [1]. These nanofluidic
systems have one or more height steps that take each channel from a starting critical
dimension (height) of ~100 nm down to as small as ~10 nm. As solution flows through
these nanochannels by capillary action, any dissolved components that are smaller than a
height step continue down the channel, while structures that are larger than a height step
are trapped at the interface. We have demonstrated that these nanofluidic arrays can
selectively capture nanoparticles and viruses at height steps in a size-selective fashion
[1,2]. We have recently begun to study the fractionation of proteins in these nanofluidic
systems. Our data show that smaller proteins, such as myoglobin and hemoglobin, can
flow through nanochannels that step down to ~15 nm, while larger proteins, such as
ferritin and thyroglobulin, tend to accumulate at the height steps. We are currently
exploring the effects of protein size and channel height on trapping. We are also
evaluating these nanofluidic systems to more accurately size-profile lipoproteins.
References:
[1] Hamblin, M.N.; Xuan, J.; Maynes, D.; Tolley, H.D.; Belnap, D.M.; Woolley,
A.T.; Lee, M.L.; Hawkins, A.R. Lab Chip 10, 173-178 (2010).
[2] Xuan, J.; Hamblin, M.N.; Stout, J.M.; Tolley, H.D.; Maynes, D.R.; Woolley,
A.T.; Hawkins, A.R.; Lee, M.L. J. Chromatogr. A 1218, 9102-9110 (2011).
Notes:
75
L-02-13
Dielectrophoresis Applied to Biomolecule Manipulation and Nanocrystal Sorting
Alexandra Ros
Arizona State University, Tempe, AZ USA
Reliable and rapid separation of proteins is both a fundamental and challenging problem
for bioanalytical and biomedical research. Conventional separation techniques reach their
limits at extremes, for example, when increased sample complexity demands for the
analysis of relevant disease markers in extremely small concentration and within a huge
background. Likewise, the separation of protein nanocrystals in heterogeneous size
fractions is little explored, however is an essential pre-requisite for successful protein
structure determination via nanocrystallography. Here, we propose and explore
dielectrophoresis as a novel migration phenomenon for biomolecules and nanocrystals in
tailored microdevices.
First, we exploit insulator-based dielectrophoresis (iDEP) for the manipulation of
diagnostically relevant proteins in DC electric fields. Streaming dielectrophoresis is
observed in DC applications using micrometer-sized posts, which allows pre-
concentration of proteins. Furthermore, focused ion beam milling is combined to standard
photolithography techniques to establish larger electric field gradients with which
proteins can be concentrated up to a factor of 45 and large DNA molecules can be
trapped under DC fields. The application of AC electric fields shows a unique
dielectrophoretic behavior at low frequency in these nanostructured devices.
Second, we use an iDEP device to sort nanocrystals of the membrane protein
photosystem I. This device features five outlets coupled to a constriction in which the
nanocrystals experience dielectrophoresis. Upon flowing through this constriction, larger
crystals are focused in a center outlet channel, whereas smaller crystals are deflected into
side channels. The analysis if these deflected crystals revealed an excellent size range of
~ 100 nm, ideally suited for nanocrystallography experiments.
Notes:
76
L-02-14
Microchip Based Methods for Monitoring Nitric Oxide Metabolites in Single Cells
and Freely Roaming Animals
Susan M. Lunte
University of Kansas, Lawrence, KS USA
Nitric oxide (NO) is a highly diffusive, reactive species that exhibits a short half-life
under physiological conditions. It is involved in many important biological processes
including immune signalling, smooth muscle relaxation and neurotransmission. Nitric
oxide synthase (NOS) is the enzyme responsible for the production of nitric oxide in vivo.
Although spectroscopic and amperometric methods are available for the detection of
nitric oxide, most suffer from chemical interferences and cross-reactivity. Therefore
most methods for the measurement nitric oxide and NOS activity are indirect, relying on
fluorescence derivatization or the measurement of substrates or products of the NOS
reaction. Nitrite, nitrate, arginine and citrulline are commonly used as indicators of NO
production. Separation-based methods particularly attractive for the investigation of
NO production and metabolism in vivo since the products of the reaction can be isolated
from each other and potential interferences. In particular microchip electrophoresis (ME)
has several advantages for the analysis of NO metabolites due to its ability to separate
charged analytes, its high separation efficiencies and short analysis times. Using
microchip electrophoresis with either fluorescence or electrochemical detection, it is
possible to measure nitric oxide, its metabolites and related biomarkers in a single run.
In these studies, microchip electrophoresis with electrochemical detection is used to
monitor NOS activity in macrophages following lipopolysaccharide stimulation. ME was
then coupled to microdialysis sampling and used to continuously monitor NO generation
in the extracellular space of tissues of a freely roaming sheep following nitroglycerin
administration. The advantages of microchip electrophoresis based methods for the
measurement of nitric oxide production in cell lysates, blood samples and in freely
roaming animals will be discussed. Authors acknowledge NIH R01NS042929 and
R21NS061202
Notes:
77
L-02-15
Integrated Microfluidic Devices for Monitoring Nitric Oxide Production in Single
Cells
Eve C. Metto; Dulan B. Gunasekara; Susan M. Lunte; Christopher T. Culbertson
Kansas State University, Manhattan, KS USA
A considerable amount of attention has been focused on the analysis of single cells to
better understand cell heterogeneity. Although microfluidic devices have several
advantages over other techniques for single cell analysis, few papers have actually
demonstrated their ability to monitor physiological changes in perturbed biological
systems. In this talk a new microfluidic channel manifold will be described that
integrates cell transport, lysis, injection, electrophoretic separation and fluorescence
detection into a single device that makes it significantly easier to analyze individual cells
at a rate of 10 cells/min. The system was employed to measure nitric oxide production in
single T-lymphocytes (Jurkat cells) using a fluorescent marker 4-amino-5-methylamino-
2’,7’-difluorofluorescein diacetate (DAF-FM DA). The cells were also labeled with 6-
carboxyfluorescein diacetate (6-CFDA) as an internal standard. The NO production by
control cells was compared to cells stimulated using lipopolysaccharide (LPS), which is
known to cause the expression of inducible nitric oxide synthase (iNOS) in immune type
cells. Statistical analysis of the resulting electropherograms from a population of cells
indicated a twofold increase in NO production in the induced cells. These results compare
nicely to recently published bulk cell analysis of NO.
Notes:
78
L-03-01
Ultra-fast, High Mass-resolution Multi-Reflection-Time-of-Flight-Mass
spectrometer as Detector for One-Dimensional and Comprehensive Two-
Dimensional Gas Chromatography: Characterization of Highly Complex Mixtures
Ralf Zimmermann1; Thomas Gröger
1; Marie Schäffer
1; Benedikt Weggler
1; Jürgen
Wendt2; Martin Sklorz
1; Theo Schwemer
1
1Univiversity of Rostock/Helmholtz Zentrum München, Munich, Germany;
2LECO
Instrumente GmbH, Mönchengladbach, Germany
Complex matrices such as petrochemical samples require highly selective analytical
methods for comprehensive analysis. The use of GC-MS and in particular of
comprehensive two-dimensional gas chromatography (GC×GC) MS nowadays is a
standard approach for resolving complex samples. Recently ultra-high mass-resolution
MS became prominent in elucidating complex samples (e.g. direct-infusion FTICR-
/Orbitrap-MS) via exact mass determination (elemental composition). This approach,
however, has limitations in generality (AP ionization selectivities/matrix effects) and
separability of isomers. By coupling of high-resolution (gas-)chromatography and high
mass-resolution MS, the knowledge e.g. on the “chemical space” of complex samples can
be further improved. A novel TOFMS-system with multi-reflection-time-of-flight
technology LECO Inc, St. Joseph, USA), allows the detection of GC-transients at high
mass-resolution (R=50.000) with good mass accuracy (<1ppm). Very fast acquisition
rates are achieved (200Hz), rendering the system for coupling to comprehensive two-
dimensional gas chromatography (GC×GC). The HRT-TOFMS (electron ionization,
70eV) was applied for analysis of e.g. petrochemical samples (one- and two-dimensional
comprehensive gas chromatography), including a B5 biodiesel (~ 5 % fatty acid methyl
esters (FAME) content). High-resolution mass spectra are used for target compound
identification/verifications (1D-GC). For comprehensive two-dimensional GC, the high-
resolution MS mode was used to improve the selectivity of a non-targeted compounds-
class identification scheme, called “scripting” [1]. The scripting approach uses two-
dimensional retention-time information (i.e. specific areas in the GC×GC-2D retention-
time-space) and substance-class specific EI-fragmentation-pattern-rules for classification
of peaks to substance classes. The high mass-resolution now enables an improved
scripting approach, using the exact mass-value of specific fragments/molecular-peaks to
suppress accidental contribution of matrix and (fragment-)peaks with different elemental
compositions. The interfering matrix-peak contribution is usually quite large in complex
sample-analysis. The exact-mass-filtering in combination with GC×GC-resolution
promise an improved understanding of complex molecular mixtures. Finally the approach
is compared to GC- FT-ICRMS. [1] W. Welthagen, J. Schnelle-Kreis, R.Zimmermann; J.
Chromatography A 1019 (2003) 233-249
Notes:
79
L-03-02
GC×GC with a Low-Power, Low-Resource, Microfabricated Thermal Modulator
Gustavo Serrano; Dibyadeep Paul; Will Collin; Amy Bondy; Katsuo Kurabayashi;
Edward Zellers
University of Michigan, Ann Arbor, MI USA
In this presentation we describe rapid, comprehensive two-dimensional gas
chromatographic (GC×GC) separations by use of a microfabricated mid-point thermal
modulator (µTM) and the effects of various µTM design and operating parameters on
performance. The two-stage µTM chip (13 x 6 x 0.5 mm) consists of two interconnected
spiral etched-Si microchannels (4.2 and 2.8 cm long) with a cross-section of 250x140
µm, an anodically bonded Pyrex cap, and a 0.3-mm-thick crosslinked wall coating of
PDMS. Integrated heaters provide rapid, sequential heating of each µTM stage at rates as
high as 2400 °C/s, while a proximate, underlying thermoelectric cooler provides
continual cooling. The average power is only 10 W for heating and 21 W for cooling
without using consumable materials. The first dimension column used for GC×GC
separations was a 6-m long, 250-mm i.d., capillary with a polydimethylsiloxane (PDMS)
stationary phase and the second-dimension column was a 0.5-m long, 100-mm i.d.,
capillary with a polyethylene glycol (PEG) phase. Using sets of 5-7 volatile test
compounds (boiling point ≤ 174 °C), the effects of the minimum (Tmin) and maximum
(Tmax) modulation temperature, stage heating lag/offset (Os), modulation period (PM), and
volumetric flow rate (F) on the quality of the separations were evaluated with respect to
several performance metrics. Best results were obtained with a Tmin = -20 °C, Tmax = 210
°C, Os = 600 ms, PM = 6 s, and F = 0.9 mL/min. Replicate modulated peak areas and
retention times were reproducible to < 5%. A structured 9-component GC×GC
chromatogram was produced, and a 21-component separation was achieved in < 3 min.
The advantages and remaining challenges to optimizing the µTM for low-resource
GC×GC separations of more complex mixtures will be discussed along with progress
toward creating a portable µGCxµGC system.
Notes:
80
L-03-03
Tandem Differential Mobility Spectrometer: An Ionization Detector for Gas
Chromatography with High Speed, Selective, Small Size and Low Cost
G.A. Eiceman; M. Menlyadiev
New Mexico State University, Las Cruces, NM USA
Electron capture and photo-ionization detectors along with flame ionization detectors are
today often replaced directly with mass spectrometers providing a second dimension of
chemical information in mass analysis. Although gas chromatography (GC)/mass
spectrometry (MS) has become affordable, routine, and reliable, disadvantages may exist
still with portability, cost in some instances, and user selection of certain analytical
parameters such as selectivity. Ion mobility spectrometry technically and practically can
bring a flexibility of user control found with ionization detectors and an additional
dimension on ion identity through mobility analysis. A functional equivalent to tandem
MS has been provided for ions at ambient pressure using a tandem differential mobility
spectrometer (DMS/DMS) for low size and cost. A first ever presentation will be given
on the function, performance, and applications of a GC/DMS/DMS.
Notes:
81
L-03-04
Screening for Chlorinated Dioxins and Furans in Soil and Sediment using Bio-
Assayand GC×GC-TOFMS, with Confirmation by GC-HRT and GC×GC-HRT
Peter Gorst-Allman1; Jayne de Vos
2; Laura Quinn
2; Claudine Roos
3; Rialet Pieters
3;
Egmont Rohwer4; John Giesy
5,6,7,8; Henk Bouwman
3
1LECO Africa (Pty) Ltd, Kempton Park, South Africa;
2National Metrology Institute of
South Africa, Pretoria, South Africa; 3North West University, Potchefstroom, South
Africa; 4University of Pretoria, Pretoria, South Africa;
5University of Saskatchewan,
Saskatoon, SK, Canada, 6Michigan State University, East Lansing, MI, USA;
7King Saud
University, Riyadh, Saudi Arabia; 8City University of Hong Kong, Kowloon, Hong Kong,
China
Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs)
are ubiquitous environmental pollutants, that are persistent and toxic, formed as by-
products of industrial and thermalprocesses. As a party to the Stockholm Convention
South Africa has the obligation to undertake appropriate research, monitoring, and
cooperation pertaining to Persistent Organic Pollutants (POPs). Currently there is no
routine PCDD/Fs laboratory in South Africa capable of these measurements. TheNational
Metrology Institute of South Africa (NMISA) in collaboration with the North-West
University has been actively investigating alternatives to the standard gas
chromatography coupled with high-resolution mass spectrometry (GC-HRMS) methods
that are used elsewhere. Our approach involves the use of bio-analytical techniques based
on in vitro transactivation assays withwhole H4IIE-luc cells as an initial pre-screen1.
Positive samples are confirmed and quantified usingtwo-dimensional gas
chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS). This
technique has been shown to be capable of reaching the levels mandated by EPA Method
1613B2,3. As part of the method confirmation results were confirmed by gas
chromatography - high resolution time of flight mass spectrometry (HRT) and by
GC×GC-HRT.Here, we outline the experiences and challenges of optimizing the
GC×GC-TOFMS method in conjunction with the H4IIE-luc bio-assay, for analysing
PCDD/Fs in South African. Advantages and limitations of the method are discussed with
reference to the first results from these methods. This integrated methodology is being
validated such that it could be implemented in other countries facing restrictions of a
developing economy and obligations under the Stockholm Convention.
Notes:
82
L-03-05
New Macroporous UHPLC Silica Particles for Biomolecular Separations
Milos V. Novotny, Benjamin F. Mann, Amanda K.P. Mann, Sara E. Skrabalak
Indiana University, Bloomington, IN USA
A new type of highly macroporous, but mechanically stable, silica particle has been
developed using a novel ultrasonic spray pyrolysis process. Spherical particles, less than
2 m size, feature an interconnected network of macropores (high intraparticle void
volume). Their high-surface area properties make them suitable for large biomolecule
separations. We have functionalized these materials with different lectins and tested their
performance and properties with standard glycoproteins and preconcentration of
important proteins from microliter volumes of biological specimens. Lectin
preconcentration has been used as a suitable prelude to high-sensitivity glycomic
profiling.
Notes:
83
L-03-06
New Polymeric Monoliths with Structure Optimized for Molecular Mass Separation
of Polymers
Alexander Kurganov; Anastasiya Kanatieva
Institute of Petrochemical Synthesis, Moscow, Russia
Monolithic columns invented in modern HPLC more than 20 years ago gained a lot of
popularity in different modes of liquid separations. The only separations of polymers
according their molecular mass were excluded from applications of monolithic columns.
The main reason for that was inappropriate monolith structure resulted in low working
column free volume used for polymer separations. Recently we have demonstrated for
monoliths based on polydivinylbenzene that monolith structure optimized can be
optimized for non-adsorbing polymer separations by varying structure of porogens used
in monolith synthesis. This technique was now extended on polar monoliths based on
poly(ethyleneglycol-dimethacrylate) and on poly(pentaerytritol acrylates). New
monoliths with optimized structure were tested in separations of polystyrene standards
and were capable with base-line separation of up to 12-14 samples of polystyrene
standards in one run. Almost linear calibration curve in the range from few million to few
hundred Daltons indicated possibility of polymer separations of a broad range of
molecular mass. Mechanism of polymer separation on polar monolithic columns appears
to be not a pure size-exclusion or hydrodynamic one and include a combination of three
contributions: size-exclusion, hydrodynamic and slalom chromatography. Non-
conventional behavior of polymers of very high molecular mass was clearly seen on
monolithic columns having small size of through pores. Varying through-pore size the
effect could be investigated even more closely than it has been done on conventional
chromatographic columns. By optimizing monolith structure and separation conditions it
was succeeded to arrive at elution profile of polymers of very high molecular mass which
is suitable for molecular mass analysis. Nevertheless, the mechanism of peak splitting of
polymers of very high molecular mass remains unexplained and requires further
investigations.
Notes:
84
L-03-07
Generating More Than 100,000 Theoretical Plates with Less Than 50 Bar in Liquid
Chromatography with Porous Pillar Arrays
Manly Callewaert1; Jeff Op De Beeck
1; Heidi Ottevaere
1; Han Gardeniers
2; Gert
Desmet1; Wim De Malsche
1, 2
1Vrije Universiteit Brussel, Brussels, Belgium;
2Mesa+ Institute for Nanotechnology,
Enschede, The Netherlands
The introduction of polymer and silica monolithic columns nearly two decades ago
created an enormous momentum to develop novel packing structures for HPLC. With
their high permeability and easy integration into longer columns, monoliths were
identified as highly suitable columns to perform high-efficiency separations.
To approach the same level of loadability as packed bed columns, our group has recently
introduced a protocol to deposit silica monolithic layers on pillar arrays. An alternative
method to generate porous layers is electrochemical anodization, which effectuates in
pores growing inwards the pillars, hence leaving the originally optimized flow profiles at
the sidewall region unaltered. The method is also more suitable to uniform porous layers
on large substrate areas.
In the present work, 300 µm wide silicon pillar array channels (diameter 5 µm, spacing
2.5 µm and height 18 µm) were anodized to render the outer 300 nm -1 µm of the pillars
surface porous. The layers were characterized with a SEM before anodic bonding to a
glass lid and appeared to be highly uniform, revealing a pore size of 30 nm. The chip was
interfaced with an on-chip detection system (5 nl injection volume), a fluorescence
microscope and a capillary HPLC instrument equipped with a 3 nl UV-Vis detection cell.
Minimal plate height (H) values on the order of 5 and 7 µm were obtained for unretained
and retained components, respectively. The required back pressure at the optimal flow
rate was below 50 bar for a 1 m long channel due to its extremely low flow resistance. H
was monitored at different positions along the channel and appeared to be constant inside
the channel, resulting in 140,000-200,000 plates at the end of a 1 m channel, enabling
excellent separations of phenones and protein digests with symmetrical peak shapes.
Notes:
85
L-03-08
Preconcentration of Aromatic Compounds in Aqueous Samples with Polymer-
Coated Fiber-Packed Capillary and the Subsequent Temperature-Programmed
Elution with Water
Yuuhi Mori1; Kenichi Nakane
1; Akira Kobayashi
1; Ikuo Ueta
2; Hayato Takeuchi
1;
Kiyokatsu Jinno1; Yoshihiro Saito
1
1Toyohashi University of Technology, Toyohashi, Japan;
2University of Yamanashi, Kofu,
Japan
Taking advantage of the excellent resistance to typical organic solvents and high
temperatures, fine fibrous materials have been introduced in separation science,
especially as the extraction medium in sample preparation and the separation medium in
chromatography [1-4]. In this work, preconcentration of aromatic compounds in aqueous
solutions was carried out with an extraction capillary packed by a bundle of polymer-
coated filaments. The extracted analytes were sequentially eluted with a flow of pure
water using temperature-programmed control of the extraction capillary. The results
suggest that the polymer-coated fiber-packed capillary could be employed as a sample
preparation technique for the analysis of water samples. Introducing the fractions eluted
from the fiber-packed capillary to conventional microcolumn liquid chromatography
(LC) system via a home-made modulator, pseudo-2D LC separations of aromatic
compounds have been demonstrated.
References
[1] Y. Saito and K. Jinno, Anal. Bioanal. Chem., 2002, , 373, 325.
[2] Y. Saito and K. Jinno, J. Chromatogr. A, 2003, 1000, 53.
[3] Y.Saito, A. Tahara, M. Imaizumi, T. Takeichi, H. Wada and K. Jinno, Anal. Chem.,
2003, 75, 5525.
[4] K.Nakane, S. Shirai, Y. Saito, Y. Moriwake, I. Ueta, M. Inoue and K. Jinno, Anal.
Sci., 2011, 27, 811.
Notes:
86
L-03-09
Identification of Unknown metabolites with Accurate Mass GC-Chemical Ionization
QTOF Mass Spectrometry
Oliver Fiehn; John Meissen; Takeuchi Kouhei; Sean Adams
University of California Davis, Davis, CA USA
Gas chromatography-mass spectrometry (GCMS) has broad compound coverage used in
metabolomic applicatons, availability of large mass spectral libraries, and reproducibility
of quantitative results. However, a large percentage of metabolites detected by GCMS
metabolite profiling methodology remain unidentified due to incomplete libraries and
lack of authentic standards. Assignment of chemical structures for unknown metabolites
is a substantial challenge in metabolomics, and an effective strategy to identify unknown
metabolites will greatly enhance the effectiveness of metabolite profiling for scientific
research. We have previously published a strategy for unknown identification using
accurate mass GCMS data, including a multi-tiered constraint process. Since then, we
have now tested this approach using standards and applied it to various research projects.
Plasma samples wereanalyzed with an Agilent 7200 series accurate-mass GC-QTOF
mass spectrometer, and electron ionization (EI) and chemical ionization (CI) data was
evaluated to determine the [M+H]+ ions of selected unknown metabolites. The Seven
Golden Rules elemental formula predictive tool was applied to determine elemental
composition, and chemical structures for predicted elemental formulas were retrieved
from the PubChem Compound Database. Retrieved structures were filtered based on
derivatization constraints and by similarity to in-silico predicted retention time and
MS/MS fragmentation to identify candidate structures. Mass accuracy measurement and
isotope abundance error were assessed for each of the three ionization methods. For all
ionization methods, average mass accuracy was < 1.8 ppm and average isotope
abundance error was < 3%. Pooled plasma from diabetic and non-diabetic human
subjects were extracted and analyzed with the Agilent 7200 GC-QTOF. Data was
acquired with a CI source with methane reagent gas and with isobutane reagent gas and
results will be discussed.
Notes:
87
L-03-10
GC and GCMS for Solar System Geochemistry and Planetary Atmospheres - Past
Missions to State-of-the-Art Instrument Development
Mark Libardoni
Southwest Research Institute, San Antonio, TX USA
Over the many years of scientific exploration throughout our solar system, gas
chromatography (GC) and mass spectrometry (MS) have played a vital role in providing
insight into geochemical processes, determining composition of planetary atmospheres,
monitoring air quality on manned space missions and even supporting long term
occupancy on the international space station. The development of high-resolution
instruments capable of meeting stringent analytical performance (sensitivity, selectivity,
speed, data file size and mass range) in addition to logistical considerations (size, mass
and power) has been a remarkable achievement. From past missions such as the Pioneer
Venus and the Mars Viking Lander to current in-flight instrumentation aboard Juno and
the Mars Science Laboratory, we shall explore the pathway that has lead to cutting edge
GC and GCMS. Recent advances in multi-dimensional separation techniques (GC×GC)
coupled with high-speed and high-resolution mass spectrometers (HRMS) is providing
scientists with unparalleled data sets that help explore and expand biochemical and
geochemical pathways. Examples of space science samples as well as laboratory based
experiments supporting organic formation in the vacuum of space will be shown and
discussed.
Notes:
88
L-03-11
Multidimensional GC Combined with Accurate Mass, Tandem Mass Spectrometry,
and Element-Specific Detection for Identification of Sulfur Compounds in Tobacco
Smoke
Nobuo Ochiai1; Kikuo Sasamoto
1; Kazuhisa Mitsui
2; Yuta Yoshimura
2; Frank David
3;
Pat Sandra3
1GERSTEL KK, Tokyo, Japan;
2JAPAN TOBACCO Inc., Kanagawa, Japan;
3Research
Institute for Chromatography, Kortrijk, Belgium
GC-MS has been an indispensable technique for identification of volatile compounds.
However, GC-MS is often insufficient for unequivocal identification of trace components
in complex samples due to co-elution of various compounds. GC-MS with simultaneous
selective detection can help locate the region of interest within the complex
chromatogram, but lack of sufficient resolution may still preclude reliable identification.
A selectable 1D/
2D GC-MS with element-specific detection can significantly improve the
identification capability as well as the resolution of complex regions [1]. With this
system, simultaneous mass spectrometric and element-specific detection can be
performed for both 1D GC and
2D GC, without any instrumental set-up change. Electron
ionization (EI) mass spectra obtained by 1D/
2D GC-MS with element-specific detection
provides additional filtering of MS library search results based on elemental information
and linear retention indices (LRI) [2]. Also, the availability of accurate mass spectra
provides additional identification power. In natural product identification, however, EI
mass spectra often lack an abundant molecular ion that is required for identification of
unknowns. In this respect, chemical ionization (CI) offers interesting possibilities,
especially in combination with tandem mass spectrometry (MS/MS) with accurate mass
detection using recently introduced GC-Q-TOF-MS technology. Accurate masses from
MS/MS product ion spectra can help verify that all the fragment ions generated can be
correlated to the proposed structure.
In this study, 1D/
2D GC-Q-TOF-MS with sulfur chemiluminescence detection (SCD) is
applied for identification of trace sulfur compounds in highly complex sample such as
tobacco smoke. Identification is based on MS library search, 2D LRI, and formula
calculation based on EI accurate mass spectra. In addition, MS/MS of protonated
molecular ion obtained from positive CI provides additional information for structure
elucidation.
References
[1] K. Sasamoto, N. Ochiai, J. Chromatogr. A, 1217 (2010) 2903.
[2] N. Ochiai, K. Sasamoto, K. MacNamara, J. Chromatogr. A, 1270 (2012) 296.
Notes:
89
L-03-12
Multidimensional Gas Chromatography and Planar Microfluidics with Tandem
Sulfur Chemiluminescence and Flame Ionization Detection for Sulfur Compounds
Analysis
Jim Luong1; Ronda Gras
1; Robert Shellie
2; Hernan Cortes
2, 3
1Dow Chemical Canada, Fort Saskatchewan, AB Canada;
2ACROSS, University of
Tasmania, Hobart, Australia; 3HJCortes Consulting LLC, Midland, TX USA
The detection of sulfur containing compounds in different hydrocarbon matrices, ranging
from light hydrocarbon feedstocks to medium synthetic crude oil feeds, provide
meaningful information for the optimization of refining processes. Multiple customized
methods are currently being employed by the petrochemical and chemical industries to
meet these analytical challenges. With the incorporation of planar microfluidic devices
in a novel chromatographic configuration, the presence of a wide range of common sulfur
compounds such as hydrogen sulfide, carbonyl sulfide, carbon disulfide, alkyl
mercaptans, alkyl sulfides and disulfides, thiophene, alkyl thiophenes, alkyl
benzothiophenes, dibenzothiophene, alkyl dibenzothiophenes and heavier distribution of
sulfur compounds over a wide range of matrices spanning across a boiling point range of
more than 650 degree C can be characterized using one single analytical configuration in
less than 25 minutes. In tandem with a sulfur chemiluminescence detector used for the
measurement of trace sulfur compounds (which offers enhanced sensitivity, selectivity,
and equi-molar response to all sulfur components) is a flame ionization detector. The
flame ionization detector can be advantageously used to establish the boiling point range
of the sulfur compounds in various hydrocarbon fractions, thereby delivering elemental
specific simulated distillation capability. System configuration and examples of industrial
applications such as sulfur odorants in natural gas, sulfur compounds in fuels and
lubricants, and complex sulfur distributions in synthetic crude feeds will be used to
illustrate the utility of the approach described.
Notes:
90
L-03-13
Combination of On-Line Sample Concentration and Mass Spectrometric Detection
in Microscale Eectrophoresis
Hiroshi Koino1; Hiroya Ota
1; Mami Oketani
1; Takayuki Kawai
2; Kenji Sueyoshi
1;
Takuya Kubo1; Fumihiko Kitagawa
3; Koji Otsuka
1
1Kyoto University, Kyoto, Japan;
2National Institute of Advanced Industrial Science,
Ikeda, Japan; 3Hirosaki University, Hirosaki, Japan
Capillary electrophoresis-mass spectrometry (CE-MS) has many advantages, including
high resolution, small consumptions of samples/reagents and rapid identification, while
the low sensitivity is still problematic. Although the sensitivity can be improved by
applications of on-line sample concentration techniques, an effective separation length is
often reduced by an injection of an injected large volume sample solution. Large-volume
sample stacking with an electroosmotic flow (EOF) pump (LVSEP), however, gives a
high sensitivity without a loss of resolution. Unfortunately, an application of LVSEP to
capillary zone electrophoresis (CZE)-MS is difficult because of the lack of an outlet
reservoir since LVSEP requires an introduction of a background solution (BGS) from the
outlet side of the capillary for pumping out the sample matrix. In this study, the sheath
liquid poured into the ESI interface was also employed as the BGS for the application of
LVSEP to CE-ESI-MS.
In experimental, the inside wall of the capillary was modified with poly(vinyl alcohol) to
suppress the EOF for applying LVSEP. The CE-MS analyses were carried out by using a
P/ACE MDQ (Beckman Coulter) connected with a 3200 Q Trap (AB SCIEX). As a BGS
and sheath liquid, 25 mM ammonium acetate in a methanol/water (50:50 v/v) mixture
solvent was pumped into the ESI interface at a flow rate of 3.0 mL/min. Sodium 2-
naphthalenesulfonate (NS), disodium 1,3-benzendisulfonate (BDS) and disodium 1,5-
naphthalene-disulfonate (NDS) were used as test analytes.
Under an optimized condition, the sheath liquid was successfully introduced into the
capillary from the ESI interface. Three aromatic sulfonic acids were analyzed in CZE-MS
with/without applying LVSEP. As a result, the analytes were 75-120-fold concentrated as
compared to conventional CZE-MS, so that the application of LVSEP could improve the
sensitivity in CZE-MS without a significant loss of the effective length.
Notes:
91
L-03-14
Separation of Carbon Dots by Capillary Electrophoresis
Luis Colon; John Vinci; Ivonne Ferrer; Zuqin Xue
University at Buffalo, Buffalo, NY USA
Luminescent carbon dots (C-dots) and other carbon nanoparticles (CNP) have gained
interest in recent years as they have been proposed as alternatives to other nanomaterials
(e.g., semiconductor quantum dots). The characteristics of such C-dots or CNP are
typically reported assuming that there is a high degree of homogeneity in the synthesized
nanomaterials. However, for the great majority of cases, CNPs have been synthesized as
a relatively complex mixture and the reported characteristics may be an agglomerate
corresponding to an average of the multitude of species in the mixture. By means of
HPLC and capillary electrophoresis (CE), using CNPs synthesized by top-down and/or
bottom-up approaches, we show that indeed the “as-synthesized” CNP exist as a
relatively complex mixture. CE of these CNP revealed anionic species with a wide range
of electrophoretic mobilities, attributed for the most part to various degrees of
carboxylate surface functionalization. The separation of these species can reveal entities
with very unique properties that could have been missed by studying the complex
mixture alone. We show that the separated species have unique luminescent absorption
and emission characteristics; separated species do not show the wavelength-dependent
photoluminescence characteristic that is a commonly assigned to C-dots. Further,
separated fractions of C-dots show to be more biologically compatible than the mixture.
Indeed, our results underscore the importance of separating the “as synthesized”
nanomaterials into individual entities in order to properly assess the fundamental
properties of such nanomaterials and establish their applicability.
Notes:
92
L-03-15
Characterization of Phosphonium-based Ionic Liquids and Their use in
Electrokinetic Capillary Chromatography
Susanne Wiedmer1; Annika Railila
1; Jana Lokajová
2; Ashley Holding
1; Alistair King
1
1University of Helsinki, Helsinki, Finland;
2Institute of Organic Chemistry and
Biochemistry, Prague, Czech Republic
Ionic liquids (ILs) are typically organic molten salts that melt below 100 oC. During the
last decade there has been much interest in ILs, mainly because of their unique properties
and characteristics. The risk of air pollution is minimized due to their negligible vapor
pressures and as such, ILs are often considered as environmentally friendly. These
attractive properties and a close to unlimited structural possibilities give ILs a great
potential for application in a variety of fields, such as biocatalysis, organic synthesis, and
extraction, and separation, of biologically relevant compounds.
The aim of the work was to get a further insight into the application of phosphonium-
based ILs for electrokinetic chromatography (EKC), as a pseudostationary phase.
Previous studies have shown the possibility of using particular phosphonium-based ILs
for separating benzene and benzene derivatives by EKC. In order to determine the
distribution constant for analytes in EKC, the phase ratio of the used pseudostationary
phase is needed. For calculation of the phase ratio the critical micelle concentration
(CMC) values for the pseudostationary phase are also required. Therefore, in this work
the goal was to determine the CMC values for phosphonium-based ILs, under conditions
that can be used for analyte separation by EKC. Another purpose of the work was to
investigate the ionicity of some phosphonium-based ILs. The ionicity can be calculated
once the temperature-dependent conductivity and viscosity of the IL are known. This can
then be plotted by the so-called Walden plot in order to compare the ionicity of ILs to
other well-known electrolytes. A deeper understanding of the ionicity of the IL may be of
importance for understanding IL and solvent, or analyte, interactions, as well as to gain a
better understanding of the physical properties of the IL, in general.
Notes:
93
L-03-16
Capillary Electrophoresis in Classical and Carrier Ampholytes-Based Background
Electrolytes Applied to Separation and Physicochemical Characterization of Peptide
Hormones
Vaclav Kasicka1; Veronika Solinova
1; Dusan Koval
1; Martine Poitevin
2; Jean-Marc
Busnel2; Gabriel Peltre
2
1Czech Academy Science., Prague, Czech Republic;
2Ecole Super de Physique et Chimie
Industrielles, Paris, France
Capillary zone electrophoresis (CZE) in classical background electrolytes (BGEs) and
carrier ampholytes-based capillary electrophoresis (CABCE) using narrow pH fractions
of carrier ampholytes (CAs) as constituents of quasi-isoelectric BGEs [1, 2] have been
applied to separation and physicochemical characterization of synthetic human and
salmon gonadotropin-releasing hormones (GnRHs) and their derivatives and fragments.
The selectivity, separation efficiency, resolution and speed of CZE and CABCE analyses
have been compared within a wide pH range of the classical BGEs (pH 1.8-11.3) and
CAs-based BGEs (pH 3.50-9.75) in their applications to separation of two mixtures of
structurally related GnRH peptides. A baseline separation of peptides was achieved both
by CZE and CABCE. Selectivity of CABCE was identical with that of CZE but CABCE
provided a faster separation and/or better resolution of some GnRH peptides than CZE. In
addition to the separation of related GnRH peptides, their effective electrophoretic
mobilities at constant ionic strength 25 mM and reference temperature 25°C were
determined and from the dependence of effective mobilities on pH, the isoelectric points
(pI), acidity constants of ionogenic groups (pKa) and ionic mobilities of the particular
ionic forms of the GnRH peptides were estimated [3]. The pI values obtained by CABCE
were in a good agreement with those determined by CZE in classical BGEs but in some
cases rather different from those predicted by theoretical calculations.
The work was supported by GACR, projects no. 203/08/1428 and P206/12/0453, and by
ASCR, research project RVO 61388963.
References 1. J.M. Busnel, F. Kilar, V. Kasicka, S. Descroix, M.C. Hennion, G. Peltre, J. Chromatogr.
A 2005, 1087, 183‑188. \
2. D. Koval, J.M. Busnel, J. Hlavacek, J. Jiracek, V. Kasicka, G. Peltre, Electrophoresis
2008, 29, 3759-3767.
3. V. Solinova, M. Poitevin, D. Koval, J. M. Busnel, G. Peltre, V. Kasicka, J. Chromatogr.
A 2012, 1267, 231-238.
Notes:
94
L-03-17
Better Sniffing – A Story of High-Resolution Wine Aroma Analysis
Sung-Tong Chin1; Graham Eyres
2; Philip Marriott
1
1Monash University, Clayton, Australia;
2CSIRO Animal, Food and Health Sciences,
Sydney, Australia
Analysis of odour-active compounds in complex samples requires effective molecular
separation from a multitude of other matrix components. Single dimensional gas
chromatography-olfactometry (GC-O) – a common screening method - exhibits
incomplete resolving capability. Integrated system having the combined capability to
perform GC, comprehensive two-dimensional GC (GC×GC) and target heart-cut
multidimensional GC (MDGC) using olfactometry (O), flame ionisation (FID) and/or
mass spectrometry (MS) detection is described. This combines contemporary GC
methods in a single instrument to provide very high resolution profiling. Initial
assessment of volatile compound composition is achieved by GC×GC-FID analysis,
correlated with GC-O. Subsequent microfluidic switching selects regions (heart-cuts)
from the first dimension column for further resolution on a long secondary column for
parallel detection using O and MS. Various operational conditions are compared; the
favoured MDGC mode involves cryotrapping of heart-cuts, cooling the oven, reducing
carrier flow then re-commencing the analysis. An analytical strategy incorporating the
above analyses with cumulative solid phase microextraction sampling for volatile
enrichment is presented. Excellent qualitative and quantitative performance was
demonstrated for a Shiraz wine, with tentative identification of acetic acid, octen-3-ol,
ethyl octanoate, β-damascenone, ethyl phenylpropanoate as aroma contributors. The
integrated system allows direct comparison among multiple GC techniques, simplifying
analytical implementation, and improving the method accuracy, for efficient
identification of unknown odorants.
Notes:
95
L-03-18
User-friendly Method for GC×GC Optimization
Pierre-Hugues Stefanuto1; Jean-Marie Dimandja
2; Jean-François Focant
1
1University of Liège, Liège, Belgium;
2Spelman College, Atlanta, USA
Almost 30 years are gone since the first paper about multidimensional GC was published
by John B. Phillips 1. After several years of developing process, Comprehensive Two
Dimensional Gas Chromatography systems are in the commercialization step of its live
time. During this period, the advantages of GC×GC, regarding to classical D1 system,
were clearly demonstrated 2. However, the new parameters involve in a GC×GC method
are still not completely understand and people don’t use it at the maximum of its
capacity. According to the literature more and more group are using GC×GC for different
kind of applications. Unfortunately, the orthogonality and the column set are most of the
time poorly optimized. In this study, we develop an user-friendly method to choose the
best column combination and the best separation parameters for a particular application.
All these developments were based on different mix of standard call the Century mix and
the Dimandja mix. These are the descendants of the Phillips mix create in 2003 by J.
Dimandja 3.
This method is based on the Retention Index obtained in a classical GC analysis and
projected in the 2D space. Using this projection method, we identified four major types of
orthogonality based on the peak dispersion obtained. We name those: Normal, Reverse,
Hybrid and Transpose orthogonality. To characterize these observations, we developed
the Orthogonality Index. Going back to the mathematical definition of orthogonality, this
factor is the angle formed between the alkane line and the aromatic hydrocarbon line in
the chromatographic space. Using this predictive tool, people should be able to choose
the best column set and to optimize easily the separation parameters.
1. Phillips, J.B. et al. Anal. Chem. 57, 2779-2787 (1985).
2. Dimandja, J.-M.D. Anal. Chem. 76, 167A-174A (2004).
3. Dimandja, J.-M D. et al. J Chromatogr a 1019, 261-272 (2003).
Notes:
96
L-03-19
Efficiency of Monolithic Capillary Columns in High Pressure Gas Chromatography
Anastasiya Kanatyeva; Alexander Kurganov; Alexander Korolev; Valeriya Shiryaeva;
Tamara Popova
TIPS RAS, Moscow, Russia
The column performance in gas and liquid chromatography is often evaluated using Van
Deemter relationship (the potential efficiency). However in practice one often needs to
know what the separation efficiency can be achieved at the definite chromatographic
conditions, or what column length is needed to get the target efficiency in the predefined
analysis time. These questions can be answered using a kinetic plot which characterizes
the kinetic efficiency of the column. The aim of the present paper is characterization of
potential and kinetic efficiency of monolithic capillary columns in high pressure gas
chromatography (HPGC). Different methods were used in the past on creating the kinetic
plots and all of them were evaluated with non-compressible mobile phases. The kinetic
plots in present study are used for analysis of kinetic efficiency of monolithic sorbents in
HPGC, i.e. with a compressible mobile phase. It is shown that values of theoretical plate
time and maximum number of theoretical plates depend significantly on monolith
structure which is determined by synthesis conditions. It is demonstrated that
construction of kinetic plots in HPGC using Van Deemter relationships required
accounting for compressibility of mobile phase. The influence of mobile phase nature on
potential efficiency of monolithic capillary column based on ethylenglycol
dimethacrylate was also studied. Model mixture of light hydrocarbons C1 to C4 was used
to find out the changes of potential efficiency and selectivity of polymeric monolithic
columns with carrier gas. Minimal value of HETP was found for CO2 or N2O carrier
gases.
Notes:
97
L-03-20
Evaluation of First Responders’ Exposure to Mixed Halogen Planar Compounds in
Fire Debris Using Comprehensive Two Dimensional Gas Chromatography
Kari Organtini1; Frank Dorman
1; Mark Merrick
2
1The Pennsylvania State University, University Park, PA USA;
2LECO Corporation, St.
Joseph, MI USA
There is developing concern over the fate of brominated flame retardants (BFRs) when
they reach the end of their life through combustion. The aftermath from large scale events
such as the Plastimet fire in Ontario, Canada and the attacks on the World Trade Centers
in New York City demonstrate the need to investigate the components of the fire debris
generated during fires. While monitoring the health of first responders at both scenes, a
higher incidence of cancer has been reported in those exposed to the debris. The role of
mixed halogenated planar compounds generated during combustion of BFR-containing
products is being investigated as to their toxicological effects.
Due to sample complexity, resulting both from sample matrix and the large amount of
possible target compounds, comprehensive GC×GC-TOFMS is the preferred technique
for this fire debris analysis. By taking advantage of enhanced peak capacity, and
decoupled separation mechanisms, halogenated planar compounds with similar structures
may be better resolved from one another, and more importantly from the matrix. Once it
has been determined what types of mixed halogen planar compounds are present in fire
debris samples, the effect of their exposure can be studied. Through the use of both
hepatic cell studies and animal dosing studies, their role in disease risk can be evaluated.
A GC×GC-TOFMS method has been developed for the characterization of fire debris
samples. Preliminary data showing the tentative identification of mixed
brominated/chlorinated dibenzodioxins and dibenzofurans, as well as a range of
polychlorinated planar compounds, including dioxins, furans, and naphthalenes will be
presented. Also, the preliminary data obtained from cell studies investigating the
toxicology of the mixed bromo/chloro dioxin and furan congeners will be described.
Notes:
98
L-03-21
From the Olympics to the North Sea Gas Fields - Using GC×GC to Investigate
Atmospheric Complexity
Richard Lidster; Jacqueline Hamilton; Alastair Lewis; Rachel Holmes; James Lee; James
Hopkins
The University of York, York, United Kingdom
Volatile Organic Compounds (VOCs) contribute to the formation of photochemical smog
and secondary organic aerosol and thus play an important role in atmospheric chemistry.
It has been shown in previous studies that a large portion of the VOC loading of urban air
is unaccounted for by traditional single column GC methods [1] and accurate
quantification is complicated by mixture complexity. The increased peak capacity of
comprehensive two-dimensional gas chromatography (GC×GC) overcomes many of the
single column limitations allowing the resolution of hundreds of species in urban air. A
key component in GC×GC is the modulator and cryogenic modulation is normally the
first choice for most analysts due to its ease of use, high reliability, sensitivity and
commercial availability. There are however a few drawbacks to using these modulators in
the field including size, cost, limited trapping temperature and cryogen use. Valve based
modulators address these problems at significantly lower cost and consumable use and
stopped flow methods overcome previous sensitivity issues [2].
A Thermal Desorption (TD) total transfer valve GC×GC-FID system has been developed
for the analysis of atmospheric VOCs [3] and has been deployed in the field. Careful
optimisation of columns flows and loop volume was required and a pre-column cryogenic
trap was used to improve sample injection. The instrument was used to measure air
quality during the 2012 Olympics, as part of the ClearfLo (Clean Air for London)
campaign. It was also used to investigate emissions downwind of the Elgin Total Oil
Platform leak using samples collected on-board the UK NERC Facility for Airborne
Atmospheric Measurements (FAAM) BAe 146 aircraft.
1. Lewis AC et al. Nature 2000, 405, 778-781.
2. Mohler RE et al. Analytica Chimica Acta 2006, 555, 68-74.
3. Lidster RT et al. Journal of Separation Science 2011, 34(7), 812-821.
Notes:
99
L-03-23
Development of a 2D LC-CE-ESI Platform for Peptide Mapping Applications
Will Black; J. Scott Mellors; J. Michael Ramsey
University of North Carolina, Chapel Hill, NC USA
The analysis of biological samples is becoming increasingly sophisticated as researchers
from a variety of disciplines seek to simultaneously characterize numerous analytes at the
molecular level. The continued expansion of proteomics, metabolomics, and many other -
omics applications serves as a salient example of this trend. Increasing the scope of
biological research necessitates improvements to existing separations methods, which are
quickly becoming a bottleneck in sample analysis. One promising method for
dramatically increasing separation performance is to perform multi-dimensional
separations, e.g., coupling orthogonal separation methods sequentially to perform 2D in
time separations. The serial coupling of separation methods is also attractive in situations
where a single detector is desirable such as electrospray ionization. Previously, our
laboratory has reported a two-dimensional separation platform based on coupling
capillary liquid chromatography (LC) with microchip capillary electrophoresis-
electrospray ionization (CE-ESI). We demonstrated the peptide mapping capabilities of
this method by characterizing glycopeptides from a monoclonal antibody digest. This
presentation will focus on the continued development of this technology by improving
the sample transfer between the two dimensions and by incorporating new data analysis
software. The sensitivity of this method can be greatly enhanced by increasing the
percentage of the LC effluent that reaches the CE separation channel. The integration of a
sample-focusing step between the LC and CE dimensions improves sample transfer by at
least an order of magnitude, resulting in a significant increase in sensitivity. Furthermore,
the utilization of better data analysis software improves the utility of this method by
generating two-dimensional maps with simultaneous access to mass spectrometry data.
Notes:
100
L-03-24
Packing and Characterization of High Aspect Ratio LC Columns in Capillaries and
Microfluidic Devices
James Grinias1; Martin Gilar
2; James Jorgenson
1
1University of North Carolina, Chapel Hill, NC USA;
2Waters Corporation, Milford, MA
USA
Over the past decade, the use of sub-2 micron stationary phase particles (both fully
porous and superficially porous) has significantly improved the performance of LC
columns. However, when these columns are packed in low aspect ratio beds (common
for capillaries and microfluidic devices), the extra-column volume of commercial
instrumentation can severely reduce the theoretical efficiency expected with these
particles. In order to reduce the impact of extra-column band broadening as well as to
allow for greater sample loading capabilities, larger aspect ratio columns (with inner
diameters on the order of 300-500 microns) can be utilized. Packing of these high aspect
ratio columns has often been difficult and has usually given lower efficiency than the
same particles with lower aspect ratios. This efficiency is decreased even more in
microfluidic devices where turns and vias can increase band broadening. Recent results
have indicated that some of the decreased efficiency of these packed beds can be
attributed to a particle size segregation effect where smaller particles are concentrated at
the column wall. This effect is particularly noticeable as aspect ratio increases and leads
to enhanced transcolumn broadening which reduces efficiency. This study will describe
progress towards improving the performance of large aspect ratio columns, packed into
both capillaries and microfluidic devices. Differences in packing were tested by varying
slurry concentration and slurry solvent to observe how efficiency was affected. How
these changes were expected to prevent particle size segregation will also be presented.
Notes:
101
L-03-25
Porous Monolithic Thin Layers for TLC-MS Separations
Alexandros Lamprou; Zhixing Lin; Yongqin Lu; Frantisek Svec
Lawrence Berkeley National Laboratory, Berkeley, CA USA
Porous polymer monoliths are applicable as stationary phases for a variety of
chromatographic modes. Among them, thin layer chromatography (TLC) is a facile and
inexpensive separation method, where the mobile phase is propagating by capillary
actuation. Owing to its flat format, TLC may be coupled with advanced mass
spectrometric (MS) detection methods. It also offers the advantage of running several
samples in parallel lines, while the developed plates can be stored for archiving.
Motivated by the increasing attention on TLC, very thin polymeric monolith layers were
prepared on glass plates and applied for the separation of biomolecules. The performance
of such thin layers is controlled by both their porous structure and surface chemistry.
Thus, styrene-based, as well as methacrylate-based layers were prepared employing both
UV- or thermally-initiated polymerizations. Their pore surface was subsequently
modified via photografting and/or attachment of functional moieties via chemical
reactions. Specifically, the styrene-based layers were hypercrosslinked by Friedel-Crafts
alkylation, in order to increase their porosity by creating a multiplicity of additional
mesopores. Hence, excellent separations of small molecules were achieved. The
methacrylate-based layers were photografted with functional monomers in a spatially
controlled fashion that enabled the formation of a diagonal hydrophobicity gradient.
During two sequential developments, 2-dimensional separations with superior resolution
and selectivity were achieved. In another implementation, gold nanoparticles were
incorporated in the thin layers, followed by a final modification with polar branched
polymer chains. Different detection methods were used for the separations assessment,
including optical methods and MS methods such as matrix-assisted laser
desorption/ionization (MALDI). It is worth mentioning that the desorption/ionization of
the separated compounds from plates containing gold nanoparticles was achieved without
the addition of any matrix, which has to be otherwise typically applied. The advantages
of eliminating the matrix include simplified sample preparation and ability to detect small
molecules.
Notes:
102
L-03-26
“Knitting” Poly(Styrene-divinylbenzene) Capillary Monoliths with Large Surface
Area via Friedel-Crafts Slkylation with External Crosslinkers
Fernando Maya Alejandro1; Frantisek Svec
2; Víctor Cerdà
1
1Universitat de les Illes Balears, Palma De Mallorca, Spain;
2Lawrence Berkeley
National Laboratory, Berkeley, CA USA
A new strategy for the enhancement of column efficiency of styrene-divinylbenzene
based monolithic capillary columns for liquid chromatography has been developed. This
approach is based on the preparation of generic poly(styrene-divinylbenzene) monoliths,
which are then hypercrosslinked using external crosslinkers under Friedel-Crafts
alkylation reaction conditions. Precursor polymers are first swollen with 1,2-
dichloroethane, and the loose polymer chains located at the pore surface are “knitted” via
reaction with an external crosslinker. Three different external crosslinkers, α;,α;′-
dichloro-p-xylene, bis(chloromethyl)-1,1′-biphenyl, and dimethoxymethane, were used
for the hypercrosslinking of monoliths. The hypercrosslinked monoliths were then
successfully applied for the separation of small molecules including acetone and
alkylbenzenes in isocratic separation mode. Hypercrosslinking afforded a significant
increase in column efficiency to more than 50,000 plates/m for retained analytes at room
temperature.
Notes:
103
L-03-27
Development of a Capillary Column Coated with C60-Fullerene for Liquid
Chromatographic Separations
Yoshiki Murakami; Takuya Kubo; Koji Otsuka
Kyoto University, Kyoto, Japan
Recently, carbon-based nanomaterials (e.g., graphene, fullerene, and carbon nanotubes)
have been investigated in many fields because of their excellent properties. They have
large delocalized π-electrons, which can form π-stacking interactions with aromatic
compounds. Therefore the carbon nanomaterials have been studied for various
applications in separation chemistry as adsorbents of solid-phase extraction and
pseudostationary phases in electrokinatic chromatography.
As one of drawbacks of carbon-based nanomaterials, the aggregation via strong π-
stacking interactions is troublesome, so they hardly dissolve and/or disperse in any
solvents. This is the major limitation of carbon nanomaterials for a practical use. Though
functionalizations of the surface of the carbon nanomaterials to improve its solubility
have been studied, it varies the superficial properties of the materials. The aim of this
study is to develop a novel separation medium in a capillary enabling a specific
separation based on π-stacking using carbon nanomaterials by immobilizing the carbon
nanomaterials onto the capillary inner wall for open-tubular capillary liquid
chromatography (OT-CLC).
C60-fullerene was employed as a stationary phase because of its better solubility and
reactivity compared to the other carbon nanomaterials. Perfluorophenyl azide (PFPA) as
a photoactive molecule was used to immobilize the C60-fullerene onto the capillary inner
wall. The conditions of immobilization of C60-fullerene were optimized and the
capillaries were evaluated by OT-CLC. As a result, benzene was retained on the coated
capillary while the other control columns showed no retention ability for benzene. These
suggested that C60-fullerene was successfully immobilized onto the capillary inner wall.
To evaluate the major interaction on the column, we analyzed both the coated capillary
and a commonly used C18 column by comparison of the separation behaviors of
alkylbenzenes and polycyclic aromatic hydrocarbons. The results suggested that π-
stacking by the C60-fullerene effected the separation on the coated capillary.
Notes:
104
L-04-01
Development of a New Capillary Column Format Utilizing Single Column and
Parallel Column Array Geometries for Improved Separations
Frank Dorman; David Gaddes; Jessica Westland; Srinivas Tadigadapa
Penn State University, University Park, PA USA
A significant amount of work has been performed on µGC in the past decade[1], [2]. This
work generally applies µGC to lab-on-a-chip type devices for separation of explosive or
hazardous compounds as a portable device[3], [4]. The majority of the previous work has
been directed toward the goal of an on-chip-GC with less focus on bringing µGC into a
typical, or “general purpose” use as an improved column.
Replacing conventional drawn fused-silica tubing by a micromachined gas
chromatography (µGC) column is attractive for a number of reasons: (i) µGC allows for
minimal thermal mass, allowing for fast temperature ramping[5], (ii) miniaturization of
the tubing allows for miniaturization of the instrument, (iii) the geometery of the µGC
allows for possibilities to significantly increase plate count [6], (iv) the backpressure of
these µGC columns tend to be lower than that of their commercial counter parts, (v)
conventional silica tubing exhibits significant variation in both inner-diameter and length
(as a finished column) thereby affecting the elution times from column to column and the
exact replication of a given separation. This final issue has been especially challenging
when attempting parallel-column array separations.
This presentation will address these limitations through the development of a new device
in both single channel, and parallel-column array formats. This device is also capable of
higher-temperature operation due to the fixturing developed in our laboratory.
Demonstration of performance will be made using conventional chromatographic probes
as well as high-temperature applications.
Notes:
105
L-04-02
Germania-Based Sol-Gel Materials in Separation Science
Abdul Malik; Chengliang Jiang; Abdullah Alhendal; Minh Phuong Tran; Emre Seyyal
University of South Florida, Tampa, FL USA
Poor pH stability is one serious shortcoming that limits applicability of traditional silica-
based materials as sorbents and/or stationary phases in chromatographic analysis. High
complexity of many sample matrices in biomedical, clinical, and environmental analyses
dictates pH manipulation during isolation, enrichment and/or separation of target
analytes. This, in turn, demands enhanced pH stability from the used support and/or
stationary phase materials. Traditional silica-based materials fail to fulfill this stability
requirement, especially under highly acidic or highly basic conditions. Significant effort
has been devoted to finding alternative materials with superior pH stability. These
include, chromatographic materials based on organic polymers as well as various metal
oxides, such as alumina, zirconia, titania, hafnia, etc. Although these materials possess
better pH stability, they have other shortcomings: (a) organic polymers often swell or
shrink depending on the nature of the solvent(s) they are exposed to, and (b) surface
chemistry of metal oxides does not allow effective bonding of organic ligands. As a
result, the search for alternative chromatographic materials continues.
Germania (GeO2) is an isostructural analog of silica (SiO2), which can be anticipated
from the fact that silicon (Si) and germanium (Ge) are nearest neighbors in group 14 of
the periodic table of elements. Naturally, properties of these two oxides are very similar,
and the surface derivatization chemistry of germania resembles that of silica. Taking all
this into consideration, recently, we introduced germania-based sol-gel organic-inorganic
hybrid materials [1-2] as sorbents for capillary microextraction [3] coupled to GC or
HPLC. An important finding was that germania-based sol-gel hybrid materials possess
exceptional pH stability [2] ranging from 0 to 14. In this presentation we will present
recent experimental findings of our laboratory on germania based GC stationary phases,
monolithic beds, and microparticles.
References:
[1] L. Fang, S. Kulkarni, K. Alhooshani, A. Malik, Anal. Chem. 2007, 79 (24), 9441-
9451.
[2] S.S. Segro, J. Triplett, A. Malik, Anal. Chem. 2010, 82, 4107-4113.
[3] S. Bigham, J. Medlar, A. Kabir, C. Shende, A. Alli, A. Malik, Anal. Chem. 2002, 74
(4), 752-761.
Notes:
106
L-04-03
Practical Reduction of Analysis Time in GC and GC/MS Using Existing
Instrumentation
Jaap De Zeeuw; Jim Whitford
Restek Corporation, Middelburg, The Netherlands
Shortening run times is a welcome exercise for many laboratories, especially when the
number of samples increase. If there is “enough” separation one can speed up separations
using shorter columns, or use the oven temperature to elute compounds quicker. A
parameter that is not used to its potential, is the gas-pressure. If there is “just enough”
separation, strategies are different as a loss of plates in not acceptable. Use of Hydrogen
is an interesting option especially since there is a helium shortage. Practical hydrogen can
speed up a factor 1.7 but user has to deal with safety. An other way is using the 0.15/0.18
mm. Such diameters allows reasonable back pressures, efficiency and practical
robustness to deal with different sample types; For both options (hydrogen and smaller
ID), the peak widths that are produced are smaller meaning that the amount injected can
be reduced. In all cases discussed, its very important to change oven temperature
program to obtain similar peak elution order. All parameters discussed will be illustrated
with practical examples.
Notes:
107
L-04-04
New Developments in Ionic Liquid GC Stationary Phases
Leonard M. Sidisky; James L. Desorcie; Greg A. Baney; Gustavo Serrano; Daniel L.
Shollenberger; Katherine K. Stenerson
Supelco, a Member of the SIGMA ALDRICH Group, Bellefonte, PA USA
Ionic liquids are a class of nonmolecular ionic solvents with low melting points. These
liquids are unique combination of cations and anions and can provide a variety of
different selectivities when used as stationary phases in capillary gas chromatography.
The majority of the polyionic ionic liquid phases that we have been evaluating all provide
polar and highly polar selectivities similar to polyethylene glycol based our
biscyanopropylpolysiloxane phases. These phases will provide unique selectivity for the
evaluation of a number of petrochemical samples. The purpose of our studies is to
determine the effects changing the cation and spacer groups on the selectivity of the
phases. Selectivity was determined and compared using various isothermal and
temperature programmed test mixes. Particular cation and anion combinations appear to
provide very unique selectivity for example shifting toluene to elute after tetradecane and
possibly coeluting with pentadecane, which demonstrates some of the highest polarity
phase selectivity we have evaluated.
Notes:
108
L-04-05
Improving Efficiency in Monolithic Capillary Column Liquid Chromatography
Pankaj Aggarwal; Kun Liu; Dennis Tolley; John Lawson; Milton Lee
Brigham Young University, Provo, UT USA
Monolithic capillary columns offer several advantages over particle packed columns,
such as high permeability, ease of preparation and, most importantly, independent
optimization of the pore and skeletal sizes. However, the chromatographic performance
of organic monoliths, in particular, has generally not reached the level of particle packed
columns, which can be attributed to the wide through-pore size distribution and variable
skeletal lattice dimensions along the column length and across the column diameter.
Synthetic methods for organic polymer monoliths have not allowed sufficient control of
pore size distribution and morphology to fully realize their full potential as stationary
phases. Characterizing the bed structures of organic monolithic columns can provide
important insights into their performance, and can aid in improving synthetic methods
through structure-directed optimization. We have been striving to improve the
performance of polymeric monoliths such as poly(ethylene glycol) diacrylate by
characterizing and optimizing the monolith morphology. We have been using statistical
principles to optimize pre-polymer compositions to obtain morphologies that lead to
improved chromatographic performance. Capillary flow porometry and three-
dimensional scanning electron microscopy have proven useful for characterizing organic
monoliths as they exist in the capillary columns and identifying the factors governing
their morphologies. As would be expected, columns exhibiting better chromatographic
performance were found to have uniform and narrow through-pore size distributions
along and across the columns. Our results emphasize the importance of developing new
approaches to optimize the monolith morphology and reduce the heterogeneity in the
columns and, more importantly, to identify the factors responsible for producing specific
monolithic structures. Different polymerization methods (e.g., living polymerization) are
being investigated for obtaining more homogenous monolithic bed structures, because
they have been reported to provide better control over polymerization conditions.
Notes:
109
L-04-06
Recent Advances in Pillar Array Column Technology
Gert Desmet; Jeff Op De Beeck; Manly Callewaert; J.G.E. Gardeniers; Wim DeMalsche
Vrije Universiteit Brussel, Brussels, Belgium
We report on the possibility to realize sub-micrometer plate heights using
chromatographic pillar array columns filled with radially elongated diamond-shaped
pillars which are 15 times wider than their axial dimension (5 µm). The use of such a
high aspect ratio pillars allows for a 5-fold reduction of the minimal plate height
compared to beds filled with pillars with a similar inter-pillar distance (2.5 µm) but with
an aspect ratio around unity (cylinders, diamonds).This increase in performance can be
attributed to a decrease in longitudinal dispersion, reflected by a reduction of the B-term
by a factor of about 25. Experiments were conducted at room temperature, as well as at
elevated temperature (70 °C), where the B-term band broadening is known to be more
critical. The concept also enables a drastic reduction of the footprint of pillar array
columns, allowing to design very long channels with a minimum of turns. Under retained
conditions, a 4 component laser dye mixture could be separated over a distance of only
1.5 mm.
Notes:
110
L-04-07
Nanoparticle-Based Sample Preparation for Biomarker Analysis by HPLC-MS/MS
Michael Lämmerhofer1, Helmut Hinterwirth
2, Elisabeth Haller
2, Wolfgang Lindner
2
1 University of Tuebingen, Tuebingen, Germany;
2 University of Vienna, Vienna, Austria
Biomarker screening in clinical analysis requires high throughput methodologies to
handle the huge amount of samples, selective and sensitive detection methods for being
capable of analyzing low abundant biomarkers, simple operational handling steps such as
pipetting only, and automatable instrumental analysis steps with high reliability, besides
of the fact that the analyzed biomarkers are meaningful and validated.
Our focus is directed to the development of assays for analyzing biomarkers of oxidative
stress in human plasma samples. Thereby, we are mainly interested in lipid (per)oxidation
and in particular of oxidation of phospholipids. The biomarker of prime interest is
oxidized low-density lipoprotein (oxLDL), which is considered a risk factor for
atherosclerosis, amongst others. The particular goal of our studies was to develop a
screening method for assessment of the oxidative stress level in human serum via
measuring the presence of oxidized phospholipids in oxLDL.
The developed method makes use of antibodies that were raised against oxLDL and
immobilized on gold nanoparticles (GNPs). The resultant anti-oxLDL-modified GNPs
are used for selective extraction and enrichment of oxLDL from human plasma samples.
After washing, the pellet is treated with methanol to extract (oxidized) phospholipids
from the trapped oxLDL. The methanolic supernatant can be used to determine the
(oxidation) profile of phospholipids in LDL via HPLC-MS/MS or MALDI-TOF.
In this presentation, the systematical study of the bioconjugation chemistry comprising
size-controlled synthesis of GNPs, surface functionalization and determination of ligand
density will be discussed in detail.
Notes:
111
L-04-09
Particulate Matter Composition as a Measure of Residential Wood Stove Emissions:
Analytical Methods and Measurements in Impacted Air Sheds
Christopher Palmer; Brittany Busby; Megan Bergauf; Tony Ward
University of Montana, Missoula, MT USA
Exposure to particulate matter (PM) and vapor phase chemical contaminants from
biomass combustion in residential settings is a significant and emerging world health
issue. It is estimated that one-half of the worlds households continue to cook and/or heat
with solid biomass fuels and that 3% of global disease can be attributed to exposures
resulting from this. There are some 8.9 million wood stoves in use in the US, with an
average annual usage per heater of 2100 hours. Eighty to 90% of the wood stoves
currently in use are old and inefficient, resulting in high levels of emissions.
Gas chromatography-mass spectrometry methods have been adapted and implemented
for the analysis of several major components of wood smoke in ambient particulate
matter. Special emphasis has been placed on quality control both in sampling and
analysis. The results reaffirm that levoglucosan is a useful chemical marker of wood
smoke particulate, and may present a relatively inexpensive alternative for quantitative
apportionment of the contribution of biomass burning to overall PM levels. Application
of the methods to the analysis of ambient air in communities where air quality is
impacted by the use of residential wood stoves leads to a greater understanding of the
source of the PM and the effectiveness of efforts to reduce PM levels. Application to the
analysis of indoor air in homes utilizing wood stoves shows very high levels of wood
smoke particulate in the homes, and dramatic reductions in the levels of particulate after
wood stoves are replaced.
Notes:
112
L-04-10
The Discovery of Attribution Signatures for Chemical Threat Agents
Carlos Fraga
Pacific Northwest National Laboratory, Richland, WA USA
Chemical threat agents (CTAs) such as highly toxic industrial chemicals and chemical
warfare agents pose a serious threat to national security. In the event that a CTA is used
in a crime or act of terrorism, there will be a need to provide evidence for attribution.
Pacific Northwest National Laboratory is developing and evaluating approaches for the
discovery and exploitation of trace impurities and constituents as chemical attribution
signatures (CAS). Our presentation will cover recent developments in the discovery of
chemical attribution signatures for CTAs studied by our group. In particular, we will
discuss our evaluation of several preprocessing software tools for locating potential CAS
in gas chromatography/mass spectrometry data. In addition, we will discuss our recent
efforts in matching chemical agents to their starting materials using trace impurities.
Notes:
113
L-04-11
Chemical and Botanical Diversity Studied through Chromatographic Analysis of
Tropical Plants Secondary Metabolites
Elena Stashenko
Industrial University of Santander, Bucaramanga, Colombia
Colombia is a privileged country, thanks to its geographical position, climate and soil
varieties, as well as enormous biodiversity. The large vegetal variety of plants and fruits,
seeds and roots, is accompanied by the immense chemical diversity of their secondary
metabolites. The study of biodiversity at the secondary metabolite level is a substantial
analytical challenge both for sample preparation and for instrumental analysis. Different
distillation methods (HD, SD, SDE, MWHD), static and dynamic headspace (P&T) and
HS-SPME, will be compared according to their sensitivity and efficiency in the study of
volatiles from Hedychium coronarium (White ginger Lily, Fam. Zingiberacea),
Posoqueria longiflora (Needle flower tree, Fam. Rubiaceae), Cestrum nocturnum (Lady
of the Night, Fam Solanaceae), Polianthes tuberosa (Tuberose, Fam. Asparagaceae),
Sansevieria guineensis (Mother-in-law´s tongue, Fam. Asparagaceae),
Brugmansia suaveolens (Angel Trumpet, Fam. Solanaceae), Cananga odorata (Ylang-
ylang, Fam. Annonaceae), and Coffea arabica (Fam. Rubiaceae) tropical flowers.
Extraction techniques with organic solvents or supercritical fluids facilitate to widen the
secondary metabolites range (e.g., of Lippia sp., plants, Verbenaceae Fam.) and to isolate,
among others, flavonoids, substances with pharmaceutical and cosmetic uses. The
combination of HPLC with various detection systems and LC-MS enables the
characterization of these mixtures and to relate their composition with antioxidant
activity. The correct botanical plant chemotype classification is possible through the
combination of statistical studies (PCA) and their secondary metabolites chromatographic
profiles, e.g., in Lippia alba and Lippia origanoides (Fam. Verbenacea) plants. This work
will show the complimentary use of extraction techniques and different chromatographic
methods (GC, GC-MS, chiral column chromatography, GC-MS/MS, GC×GC-MS,
HPLC, LC-MS), to thoroughly characterize chemical diversity (secondary metabolites) of
tropical plants of botanical and economic interest.
Notes:
114
L-04-12
Sulfur Response Characteristics of a Novel Multi-Flame Photometric Detector for
GC
Kevin Thurbide; Adrian Clark
University of Calgary, Calgary, AB Canada
The flame photometric detector (FPD) is widely used as a selective detector for sulfur
compounds in gas chromatography. However, its major limitations include the severe
signal quenching that occurs when small amounts of hydrocarbons co-elute with target
analytes, and the relative lack of a uniform response factor over a wide range of
compounds. In recent years, we have introduced a novel Multi-Flame Photometric
Detector (mFPD) that is based essentially on many flames operating in-series within a
burner. Analytes carried with GC effluent pass through these flames and their emission is
recorded in the terminal analytical flame. In terms of response, the mFPD has
demonstrated that it is significantly less susceptible to hydrocarbon quenching than a
conventional FPD, but yields a comparable sensitivity to the latter device. In this
presentation, a closer look at the mFPD response characteristics towards sulfur
compounds will be examined and new modes of operation that present a more uniform
response will also be discussed.
Notes:
115
L-04-13
Method Development of Two-Dimension Liquid Chromatography and its
Practicability in Separating Complex Samples
Qin Yang; Xianzhe Shi; Shuangyuan Wang; Lizhen Qiao; Yuanhong Shan; Xin Lu;
Guowang Xu
Dalian Institute of Chemical Physics, CAS, Dalian, China
Multidimensional liquid chromatography (MD LC), which can offer higher peak capacity
than its conventional one-dimensional counterpart, is getting the more and more
attention of chromatographists. To realize MD LC, the orthogonality of separations on
two-dimensions is the most important. The orthogonality can be adjusted by changing the
stationary phases and/or mobile phases. In the meantime, the properties of separated
components should be considered. In our recent work, several two-dimensional systems
with the different column combination modes have been developed including normal-
phase x reversed-phase liquid chromatography (NPLCxRPLC), hydrophilic interaction
chromatography (HILIC) xRPLC (HILICxRPLC), RPLCxRPLC, HILICxHILIC, silver
ion LCxRPLC, and HILIC+RPLC for different analytical aims.
In this work, to investigate the effect of the first dimensional (1st D) analysis on the LC x
LC method, three RP x RP analysis with different 1st D analysis and the same 2nd D
analysis were performed and the result revealed that an optimized 1st D analysis can
tremendously reduce the total analysis time. Further optimization was carried out on 2nd
D analysis to construct an effective RP x RP method. Ultra-high pressure LC and high
temperature LC were performed as potential 2nd D analysis and high temperature was
found to have a more significant influence on both separation efficiency and speed.
Constructed RP x RP system is used to analyze flavonoids, its advantages and
disadvantages are discussed. Further, 2DLC for lipidomics is also explored.
Notes:
116
L-04-14
High Peak Capacity Separations of Biologically-Important Molecules by Using
2DLCxUHPLC
Paola Donato1, 2
; Francesco Cacciola3, 4
; Paola Dugo1, 2
; Luigi Mondello1, 2
1C.I.R., University Campus Bio-Medico of Rome, Rome, Italy;
2SCIFAR, University of
Messina, Messina, Italy; 3SASTAS, University of Messina, Messina, Italy;
4Chromaleont
s.r.l., Messina, Italy
The high complexity of many natural samples, especially foodstuffs, often overwhelms
the separation capability of any one-dimensional LC techniques, given the high number
of compounds that may be found, with high degree of structural similarity. In such
situations, co-elutions are likely to occur, rendering detection difficult and quantification
hampered. The employment of multidimensional chromatographic techniques may
represent a viable tool in order to improve both peak capacity and the identification
power, especially in the “comprehensive” (LCxLC) mode, in which the entire analyte
sample is subjected to the “2D advantage”. Although posing more stringent requirements,
the combination of normal-phase (NP) and reversed phase (RP) represents one of the
most orthogonal approaches, maximizing the peak capacity of a 2D separation system.
On the other hand, the use of RP in both dimensions alleviates technical challenges, while
orthogonality can be tuned by different stationary phase selectivity and mobile phase
composition. Enhanced separation power can be exploited through the serial coupling of
more LC columns, under UHPLC conditions or using elevated temperatures. Whenever
the high sample complexity requires high separation power in 2D, the stop-flow
operation mode may be convenient over the continuous one. Selected applications for the
analysis of bioactive molecules in foodstuffs are illustrated, and the instrumental/software
aspects involved in the development of LCxLC techniques discussed.
Notes:
117
L-04-15
On-line Coupling of Size Exclusion Chromatography with Mixed-Mode Liquid
Chromatography for Comprehensive Profiling of Biopharmaceutical Drug Product
Yan He; Olga Friese; Qian Wang; Laura Bass; Michael Jones
Pfizer, Inc., Chesterfield, MO USA
A methodology based on on-line coupling of size exclusion chromatography (SEC) with
mixed-mode liquid chromatography (LC) has been developed. The method allows for
simultaneous measurement of a wide range of components in biopharmaceutical drug
products. These components include the active pharmaceutical ingredient (protein) and
various kinds of excipients such as cations, anions, nonionic hydrophobic surfactant
and hydrophilic sugars. Dual short SEC columns are used to separate small molecule
excipients from large protein molecules. The separated protein is quantified using a UV
detector at 280 nm. The isolated excipients are switched, online, to the Trinity P1
mixed-mode column for separation, and detected by an evaporative light scattering
detector (ELSD). Using a stationary phase with 1.7 mm particles in SEC allows for the
use of volatile buffers for both SEC and mix-mode separation. This facilitates the
detection of different excipients by ELSD and provides potential for online
characterization of the protein with mass spectrometry (MS). It is the first time that four
different chromatographic separation modes (size, cation exchange, anion exchange and
reverse phase) are combined on-line to provide the comprehensive profiling of diversified
components in a formulated biopharmaceutical drug product. The method has been
applied to quantitate protein and excipients in different biopharmaceutical drug products
including monoclonal antibodies (mAb), antibody drug conjugates (ADC) and vaccines.
Notes:
118
L-04-17
A Portable Microfabricated GC×GC for Vapor Sampling and Analysis
R. J. Simonson1; D.H. Read
1; A.W. Staton
1; J.J. Whiting
2
1Sandia National Labs, Albuquerque, NM USA;
2Three Degrees of Separation, Inc.,
Dayton, OH USA
Detection of chemical warfare (CW) agents, or other toxic vapors that could be released
as a result of industrial processes, accidents, or terrorist activity, presents a combination
of engineering challenges. The ideal instrument for on-site field analyses of toxic gases
would be small, light, portable, fast, very sensitive, cheap, capable of extended operation
on a small battery, and would require no particular training or skill on the part of the
operator. Further, the ideal instrument would be able to identify a wide range of threat
compounds, but would also never display any false alarms. Such false alarms present a
severe logistical burden for military operations and a possible source of panic in civilian
operations. This presentation will describe Sandia’s efforts to develop a high speed
fieldable analyzer system incorporating microfabricated sample collection and injection
components in combination with a flow-modulated comprehensive 2-dimensional gas
chromatograph. Severe engineering requirements are driven by the need for rapid sample
collection and analysis, low limits of detection for toxic target compounds, and limited
available power and carrier gas supply. These challenges have motivated Sandia’s effort
to develop a series of microfabricated gas valves to enable high-speed GC injection while
maintaining low sample split ratios. Recent efforts have concentrated on modifying our
initial system design to enable increased device yield while reducing carrier gas flow,
both for logistical reasons and to limit pumping requirements. Modeling of GC
performance vs. carrier gas flow, as well as empirical performance of microfabricated
GC×GC and valve components will be discussed.
Sandia National Laboratories is a multi-program laboratory managed and operated by
Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the
U.S. Department of Energy’s National Nuclear Security Administration under contract
DE-AC04-94AL85000.
Notes:
119
L-04-18
Advances in Micro and Nano-Fabricated Silicon Devices for Gas Chromatography
Joshua Whiting
3 Degrees of Separation, Inc., Dayton, OH USA
As advances in silicon fabrication and manufacturing occur, so do new opportunities in
gas chromatography. Microfabricated (MEMS) GC columns have been in development
for over 35 years with researchers primarily focusing on reproducing traditional wall
coated open tubular (WCOT) columns. The primary benefit of WCOT columns is
reduced pressure drop per unit length. This enables the use of longer columns at
reasonable inlet pressures. This results in improved resolution of complex samples. The
problem is that these longer columns cannot be practically realized with microfabricated
columns. Typical MEMS GC column lengths range from 0.5 to 3m. This is largely
dictated by the wafer size limitations of the tools used to manufacture them. At these
column lengths WCOT columns may not produce the best separations. Performance for
new (and revisited) column designs will be presented, utilizing both conventional GC
detectors and novel Nano-Resonator detector arrays developed by Analytical Pixels
Technology.
Notes:
120
L-04-19
A Micro Discharge Device as a Low Power Universal Multi-Channel Detector for
Portable and MEMS Gas Chromatographs
Adam McBrady
Honeywell ACS, Plymouth, MN USA
This talk will present Honeywell’s development of a micro discharge device (MDD) as a
detector for various gas chromatograph (GC) applications. The MDD detector collects
multi-wavelength optical emission spectra as a function of elution time. The MDD
creates a discharge at the exit of a chromatography column that is capable of exciting
analyte gases as they elute. Upon relaxation, the analytes emit characteristic frequencies
of light that are collected and recorded by a fiber optic coupled spectrometer. The talk
will describe and discuss general MDD function, strengths and weaknesses of multiple
prototype designs, and initial data sets collected.
Notes:
121
L-04-20
Microfluidic Western Blot
Robert Kennedy
University of Michigan, Ann Arbor, MI USA
Western blot is a workhorse method in biochemical sciences. In the method proteins are
separated by SDS-PAGE, transferred to a membrane, and the resulting blotted proteins
probed with antibodies for detection. The method provides selectivity based on size and
immunoaffinity for semi-quantitative protein detection. Weaknesses of the method are
lack of automation and long time requirements. We describe an approach that greatly
miniaturizes and offers potentially high throughput Western blot. In the method, proteins
are separated by sieving on a microfluidic chip in < 2min. The chip is pressed against a
membrane so that proteins are captured as they exit the chip. They are then probed on the
membrane for immunoaffinity. The use of microfluidic protein separation allows multiple
separation tracks to be deposited on the membrane either sequentially or in parallel for
potential high throughput. The method is readily automated and compatible with small
samples.
Notes:
122
L-04-21
Rapid Isolation of High Solute Amounts by Using an On-line 4D Chromatographic
System (Prep LC-GC-GC-GC)
Danilo Sciarrone1; Sebastiano Pantò
1; Peter Quinto Tranchida
1; Paola Dugo
1, 2; Luigi
Mondello1, 2
1SCIFAR, University of Messina, Messina, Italy;
2University Campus Bio-Medico of
Rome, Rome, Italy
The collection of nanalytes from natural sources is the goal of each preparative system.
Although wide-bore columns (0.53 mm I.D.) are commonly used, providing an enhanced
sample capacity, an excess of on-column sample amounts will result in skewed peaks and
decreased resolution. On the other hand, the collection of pure components requires the
injection of lower amounts in order to avoid coelutions on the wide-bore column; as a
consequence, the collection of highly pure components, at the milligram level, requires
an increased total collection time. A prep-MDGC system was successfully used for the
collection of pure components ranging from 10 to 30% concentration, collected at the
milligram level, to allow a further characterization by means of other techniques (NMR,
vapor-phase IR, MS). The demands for the collection analytes at concentrations <10%,
would consist in an increased sample injection volume, but this option could lead to the
exceed the GC liner capacity. To improve the capability of the system, an on-line 4D
chromatographic system (prep LC-GC-GC-GC) instrument was developed. Such a
system enabled the injection of higher sample volumes, the reduction of collection times,
while maintaining high levels of purity. The system consists of an LC pre-separation step,
followed by the transfer of the isolated fraction(s), to a large volume injector in the first
GC instrument, by means of an LC-GC syringe-based interface. An SLB-5ms -
Supelcowax 10 - SLB-IL59 ionic liquid stationary phase (0.53 I.D.) combination was
used in the three GC dimensions, in order to provide three distinct selectivities. A
preparative station, connected at the 3rd GC column outlet, allowed the recondensation of
pure components in a tube.
Acknowledgments
The Project was funded by the “Italian Ministry for the University and Research
(MIUR)” within the National Operative Project “Hi-Life Health Products from the
industry of foods”. Project ID: PON01_01499.
Notes:
123
L-04-22
Tagging Strategies for Capillary LC-MS Carbonyl Metabolomics
James Edwards
Saint Louis University, St Louis, MO USA
The detection, identification and quantification of the collection of small organic
molecules in a biological sample are broad and deep analytical challenges. Given the
vast number of metabolites and the wide ranges of their concentrations, current methods
of untargeted analyses cannot hope to analyze the entire metabolome. Rather our
approach will be to extract specific classes of molecules from the remaining metabolic
milieu. This is expected to enhance the sensitivity of those classes of molecules believed
to be relevant to the biological system. Specific classes of molecules will be tagged
based on functionality for analysis by mass spectrometry (MS). Multiple tags have been
synthesized and utilized to both extract these specific classes of metabolites as well as
enhance ionization efficiency. Coupling high efficiency capillary liquid chromatography
to MS analyses proves critical to resolving structural isomers and differentiating
subclasses of extracted metabolites. Isotope and isobaric tagging in addition to extraction
tags will be discussed. These methods will determine metabolic effects of high glucose
stimuli in endothelial cells as a model of diabetic complications.
Notes:
124
L-04-23
Ultrahigh Performance Capillary LC Using Submicrometer Silica Particles
Mary Wirth
Purdue University, West Lafayette, IN USA
We are investigating protein RPLC for 470 nm nonporous silica particles packed in
capillaries. These for colloidal crystals, which give plate heights below 100 nm and flow
enhancements on the order of five-fold by virtue of slip flow. The separation lengths are
3 cm, allowing for high speed protein separations with a nanoUHPLC. The LCMS of
protein mixtures is enabled by pulling the end of the capillary to a small tip, giving stable,
fritless nanospray directly from the end of the separation medium. These capillaries are
shown to give significant improvement in peak capacity and sensitivity for protein
nanoLC-MS, which promises to advance top-down proteomics.
Notes:
125
L-04-24
Packing Capillary LC Columns with sub-2 micron Particles: Everything I Know is
Wrong
James Jorgenson; Edward Franklin; Laura Blue; James Grinias
University of North Carolina, Chapel Hill, NC USA
If one contemplates increasing the operating pressures in ultra high pressure liquid
chromatography (UHPLC) to the range of 1,000 to 4,000 bars, particles around 1 micron
size should be close to optimum for separations of small molecules. Larger molecules
such as peptides and proteins should benefit from even further reductions in particle size.
Smaller diffusion coefficients of larger molecules decrease the optimum mobile phase
velocity for a given particle size, resulting in lower required pressures. These lower
pressures can be traded for the possibility of using smaller particles with these larger
molecules. Particles of approximately 0.8 micron would be desirable for use with
peptides, while particles as small as 0.5 micron could prove useful with proteins.
We have had success packing capillary columns with non-porous reversed phase particles
as small as 0.9 microns. In the case of porous reversed phase particles, however, we have
had good results with particles only as small as 1.5 microns. Attempts to pack 1 micron
porous particles have resulted in columns of inferior performance. Our past efforts have
focussed on identifying slurry solvents that are the most effective at eliminating particle
aggregates and dispersing the particles as individuals. Methods for the slurry packing of
micron-sized particles, and preparation and characterization of columns packed with
these particles, will be described.
Notes:
126
L-04-25
Capillary Electrophoresis for Deep and Accurate Bottom-up Proteomics
Norman Dovichi
University of Notre Dame, Notre Dame, IN USA
We are investigating capillary electrophoresis as an alternative technology for bottom-up
proteomics. We developed a rugged and sensitive CE-ESI interface based on
electrokinetically-pumped sheath-flow (1). This interface operates in the nanospray
domain, produces low-attomole detection limits for capillary electrophoresis separation
of peptides, and offers great flexibility in separation buffer conditions (1-2). We then
analyzed the secreted protein fraction of M. marinum (3). CZE produced slightly more
protein identifications in a slightly shorter time period than UPLC. 140 protein groups
were identified by CZE-ESI-MS/MS in three hours from this sample. We have recently
improved the system. In the single-shot analysis of the E coli proteome, we identified
>1,300 peptides and >300 protein groups in a 50-min CZE separation. We have
employed this separation system to analyze seven fractions from the E. coli proteome (4).
This system produced 23,706 peptide spectra matches, 4,902 peptide IDs, and 871 protein
group IDs in 350 min analysis time. We have also coupled CZE with multiple reaction
monitoring for analysis of zeptomole amounts of peptide (5). In an alternative separation
scheme, we employed capillary isoelectric focusing for the analysis of host-cell proteins
in commercial biopharma products; this system identified 37 host cell proteins in a total
sample preparation time of 4 hours (6). We have recently employed cIEF for the
quantitative analysis of protein expression changes in PC12 cells that have undergone
differentiation following treatment with nerve growth factor. This analysis identified 835
protein groups and produced 2,329 unique peptides IDs. 96 differentially expressed
proteins were identified. Final
1. Wojcik et al. Rapid Commun Mass Spectrom. 2010; 24:2554-60
2. Wojcik et al. Talanta. 2012;88:324-9
3. Li et al. Anal Chem. 2012; 84: 1617-22
4. Unpublished
5. Li et al. Anal Chem. 2012; 84: 6116-21.
6. Unpublished.
Notes:
127
Capillary Electrophoresis
P-201-T
A Study on the Conversion of Methanol to Formaldehyde in the GC Injection Port Chee Leong Kee
1; Min Yong Low
1; Laura Ciolino
2
1Health Sciences Authority, Singapore, Singapore;
2USFDA Forensic Chemistry Center,
Cincinnati, OH USA
P-202-W
Latex Nanoparticle Pseudo-Stationary Phases for Electrokinetic Chromatography:
Versatile Chemistry Presents Opportunities for Improvements in Performance Christopher Palmer; Andre Umansky; Jesse Hyslop
University of Montana, Missoula, MT USA
P-203-T
Metabolic Profiling Analysis of Tissues Based on CE-TOF/MS Jun Zeng; Chunxiu Hu; Peiyuan Yin; Jieyu Zhao; Guowang Xu
Dalian Institute of Chemical Physics, CAS, Dalian, China
P-204-W
Determination of Dietary Omega-3 and Omega-6 Fatty Acids in Food by Capillary
Electrophoresis Kingsley Donkor; Laiel Soliman; John Church; Bruno Cinel; Dipesh Prema
Thompson Rivers University, Kamloops, BC, Canada
P-205-T
Applicability of Capillaries CovalentlyBound with Phospholipid Vesicles to Open-
Tubular Capillary Electrochromatography-Mass Spectrometry Heidi Tiala
1; Marja-Liisa Riekkola
1; Susanne Wiedmer
2
1Laboratory of Analytical Chemistry, Department of Chemistry, University of Helsinki,
Helsinki, Finland; 2Department of Chemistry, University of Helsinki, Helsinki, Finland
P-206-W
Dual-Electrode Electrochemical Detection for Microchip Electrophoresis:
Voltammetric Identification of Chemically Labile Species Dulan Gunasekara
1; Pann Pichetsurnthorn
1; Diogenes do Santos
1, 2; Christopher
Culbertson3; Susan Lunte
1
1University of Kansas, Lawrence, KS USA;
2Federal University of Alagoas, Maceio,
Brazil; 3Kansas State University, Manhattan, KS USA
128
P-207-T
Sensitive Determination of Anions in Highly-Saline Oilfield Waters by Indirect
Photometric Capillary Electrophoresis Kingsley Donkor
1; Laiel Soliman
1; Kenneth Schmidt
2; John Crabtree
3
1Thompson Rivers University, Kamloops, BC, Canada;
2Wilson Analytical Services Inc.,
Sherwood Park, AB, Canada; 3HJC Consulting Inc., Edmonton, AB, Canada
129
Gas Chromatography
P-210-W
Response of Regulated Chlorinated Pesticides in Drinking Water Using an Ultra
Inert Column Roberto Cabrera
Clinical Laboratory of San Bernardino, Inc., Grand Terrace, CA USA
P-211-T
CZC-GC Miniaturized Analysis of POPs in 20µL Blood Benjamin L'homme; Jean-François Focant
University of Liège, Liège, Belgium
P-212-W
The Inert Flow Path: a Vital New Tool for Trace Analyses in the Gas Phase Ken Lynam
Agilent Technologies., Wilmington, DE USA
P-213-T
Fast GC-MS Analysis of Semi-Volatile Organic Compounds: Migrating from
Helium to Hydrogen as a Carrier Gas in EPA Method 8270 Jessie Butler; Alexander Semyonov; Massimo Santoro; Patrick O’Brien
Thermo Fisher Scientific, Rodano, Italy
P-214-W
Method Development for a Simple and Reliable Determination of PCBs in Mineral
Insulting Oil by SPME-GC-ECD Massimo Santoro
1; Sergio Guazzotti
1; Danilo Pierone
2; Alexandre Souza
3; Jaqueline
Lorena3
1Thermo Fisher Scientific, Rodano, Italy;
2Nova Analitica, San Paulo, Brazil;
3AES, San
Paulo, Brazil
P-215-W
Consolidated GC-MS/MS Analysis of OCPs, PAHs, and PCBs in Environmental
Samples David Steiniger; Inge de Dobbeleer; Massimo Santoro; Paul Silcock; Joachim
Gummersbach
Thermo Fisher Scientific, Rodano, Italy
130
P-216-W
A New Column Optimized for Sulfur Selective Detection Allen Vickers
1; Mitch Hastings
1; LiYing Yu
1; Gary Lee
1; Jim Luong
2; Ronda Gras
2;
Myron Hawryluk2
1Agilent Technologies, Folsom, CA USA;
2DOW Canada, Fort Saskachewan, AB,
Canada
P-217-W
PLOT Columns with Integrated Particle Trapping Yun Zou; Jan Peene; Allen Vickers; LiYing Yu; Gary Lee
Agilent Technologies, Folsom, CA USA
P-218-T
An Evaluation Ionic Liquid Capillary Columns for the FAME Isomer Analysis Leonard M. Sidisky; Greg A. Baney; Katherine K. Stenerson; Gustavo Serrano; James L.
Desorcie; Daniel L. Shollenberger
Supelco, a Member of the SIGMA ALDRICH Group, Bellefonte, PA USA
P-219-W
Considerations for Choosing a Different Carrier Gas in Gas Chromatography Jaap De Zeeuw
Restek Corporation, Middelburg, The Netherlands
P-220-W
Deactivation of Metal Capillary Columns: Moving from Trace Sulfur Applications
to Stable and Inert High Temperature GC Solutions Jaap De Zeeuw
Restek Corporation, Middelburg, The Netherlands
P-221-T
Application of High Retentive Porous Polymers in Miniaturized Systems for
Analysis of Gases in Seconds Jim Whitford
1, 2; Jaap De Zeeuw
1, 2; Bill Bromps
3; Chris van Tilburg
4
1Restek Corporation, Middelburg, The Netherlands;
2Restek Corporation, Bellefonte, PA
USA; 3Restek West, Sacramento, CA USA;
4C2V ThermoFisher, Enschede, The
Netherlands
P-222-W
A Comprehensive Solution for Drinking Water and Waste Water Analysis Using
SBSE-GC×GC-TOFMS David Benanou
Veolia Environment, Maisons Laffitte, France
131
P-223-W
A “Pseudo”-Targeted Method Based on Gas Chromatography-quadrupole Mass
Spectrometry for Plant Metabolic Profiling Investigation Yanni Zhao; Yanli Li; Yuwei Chang; Junjie Zhang; Chunxia Zhao; Xin Lu; Guowang Xu
Dalian Institute of Chemical Physics, CAS, Dalian, China
P-224-T
An Approach to Quantifying Petroleum Ether in Active Pharmaceutical Ingredients Jana Stavova; Curtis Tinker; Michelle Kubin; William Fish
Bristol-Myers Squibb Company, New Brunswick, NJ USA
P-225-W
Detection of Sildenafil Residues in Different Types of Gingseng Products with
GC/MS Turgay Celik; Enis Macit; Ahmet Turan Isik; Hüsamettin Gul; Ahmet Turan Isik;
K.Gökhan Ulusoy
Gulhane Medical Faculty, Ankara, Turkey
P-226-T
Sulfur Response in a Multiple Flame Photometric Detector Adrian Clark; Kevin Thurbide
University of Calgary, Calgary, AB Canada
P-227-W
Applications of High-Temperature GC - High-Resolution Time-of-Flight Mass
Spectrometry in Food Analysis Sjaak de Koning
1; Hans-Gerd Janssen
2, 3
1LECO Instrumente GmbH, Mönchengladbach, Germany;
2Unilever, Vlaardingen,
Vlaardingen, The Netherlands; 3University of Amsterdam, Amsterdam, The Netherlands
P-228-T
Identification of Danube Pollution Sources in Novi Sad Municipality using GC-MS
Screening Analyses Ivan Spanik
1; Olga Vyviurska
1; Alexandra Pazitna
1; Jelena Radonic
2; Maja Turk-
Sekulic2; Mirjana Vojinovic Miloradov
2
1Institue of Analytical Chemistry, Bratislava, Slovakia;
2Faculty of Technical Sciences,
Novi Sad, Serbia
P-229-W
Thermal Desorption - Gas Chromatography-Mass Spectrometry in Polyolefin
Analysis Emmanuel Yaw Osei-Twum; Jalal Bahri
Saudi Basic Industries Corporation, Riyadh, Saudi Arabia
132
P-230-T
Characterization of Novel Materials for Microfluidic Gas Chromatography Ernest Darko; Kevin B. Thurbide
University of Calgary, Calgary, AB Canada
P-231-W
Comparison of Different Types of Vegetable Oils by GC×GC-TOFMS Olga Vyviurska; Nikoleta Jánošková; Ivan Špánik
Institute of Analytical Chemistry, Bratislava, Slovakia
P-232-T
GC Separation of Alkyl Esters of 2-CN, 2-BR Carboxylic Acid Enantiomers on 6-
Tertbutyldimethysilyl-2,3-Di-Methyl (Ethyl, Propyl)-β- AND 6-
Tertbutyldimethysilyl-2,3-Di-Ethyl-γ- Cyclodextrin Stationary Phases Darina Kačeriaková; Ivan Špánik
Institue of Analytical Chemistry, Bratislava, Slovakia
P-233-W
Identification of Unique Volatile Organic Compounds in Acacia Honey by GC×GC-
TOF-MS Nikoleta Jánošková; Antónia Janáčová; Ivan Špánik
Institute of Analytical Chemistry, Bratislava, Slovakia
P-234-T
Flow Modulated Targeted Signal Enhancement forVolatile Organic Compounds Taylor Hayward; Ronda Gras; Jim Luong
Dow Chemical Canada, Fort Saskatchewan, AB Canada
P-235-W
Comparative Study of GC×GC-NCD and GC-IT-MS/MS for Determining Nicotine
and Carcinogen Organic Nitrogen Compounds in Thirdhand Tobacco Smoke Noelia Ramírez
1; Mustafa Özel
1; Alastair Lewis
2; Jacqueline Hamilton
1; Rosa Maria
Marcé3; Francesc Borrull
3; Laura Vallecillos
3
1University of York, York, United Kingdom;
2NCAS, The University of York, York, United
Kingdom; 3Universitat Rovira i Virgili, Tarragona, Spain
P-236-T
Analysis of Polymer Extracts by Gas Chromatography - High Resolution Time-Of-
Flight Mass Spectrometry with Electron Impact and Chemical Ionization David E. Alonso; Joe Binkley
LECO Corporation, St. Joseph, MI USA
133
P-237-W
GC - TOFMS Analysis of Incurred Pesticides Found in Food Commodities Frank Dorman
1; Ashley Gates
1; Elizabeth Humston-Fulmer
2; Chris Solloway
1; Joe
Binkley2; Jessica Westland
1
1Pennsylvania State University, University Park, PA USA;
2LECO Corporation, St.
Joseph, MI USA
P-238-T
Multi-Dimensional Gas Chromatography with a Planar Microfluidic Device for the
Characterization of Volatile Oxygenated Organic Compounds Ronda Gras
1; Jim Luong
1, 2; Hernan Cortes
2; Robert A. Shellie
2
1Dow Chemical Canada, Fort Saskatchewan, AB Canada;
2ACROSS, University of
Tasmania, Hobart, Australia
P-239-W
A High Performance GC Capillary Column for Challenging Industrial Applications Kaelyn Gras
1; Ronda Gras
2; Taylor Hayward
2; Jim Luong
2
1Archbishop McDonald School, Edmonton, AB Canada;
2Dow Chemical Canada, Fort
Saskatchewan, AB Canada
P-240-T
Analysis of Oxygenates in Mixed C4 Hydrocarbon Streams by Agilent J&W
PoraBOND Q PT Column Minji Cao
1; Zhaoxia Liu
1; Yun Zou
2; Jan Peene
2
1Shanghai SECCO Petrochemical Co, Shanghai, China;
2Agilent Technologies,
Shanghai, China
P-241-W
Study of Volatile Compounds of Champenoise Sparkling Wines Produced with Free
and Immobilized Yeast Gustavo Costa
2; Karine Nicolli
1; Cláudia Zini
1; Vitor Manfroi
2
1Instituto de Química,UFRGS, Porto Alegre, Brazil;
2Instituto de Ciência e Tecnol de
Alimentos, UFRGS, Porto Alegre, Brazil
P-242-T
What's in Your Beer? GC/MS Static Head Space with a Highly Inert 624 Capillary
GC Column Ken Lynam
Agilent Technologies., Wilmington, DE USA
P-243-W
Application of Full Evaporation Dynamic Headspace and Selectable 1D/
2D GC-
O/MS with Preparative Fraction Collection to Odor Analysis in Green Tea Kikuo Sasamoto; Nobuo Ochiai
GERSTEL KK, Tokyo, Japan
134
P-244-T
Novel Large Volume SPME Cartridges for Improved Sensitivity in Aroma
Measurements in Wine Thomas Robinson; Daniel Cardin
Entech Instruments, Inc., Simi Valley, CA USA
P-245-W
SPE GC-HR ToF MS Analysis of Pesticides in Olive Oil: Comparison with GC-
MSMS Mariosimone Zoccali
1; Flavio Franchina
1; Simona Salivo
1; Sebastiano Pantò
1; Peter
Tranchida1; Luigi Mondello
1, 2
1SCIFAR, University of Messina, Messina, Italy;
2C.I.R., University Campus-Biomedico
of Rome, Rome, Italy
P-246-W
Combining Liquid Chromatography and Comprehensive Two-dimensional Gas
Chromatography-Mass Spectrometry: A Powerful Approach for the Determination
of Mineral Oil Food Contamination Danilo Sciarrone
1; Mariosimone Zoccali
1; Flavio Franchina
1; Peter Quinto Tranchida
1;
Luigi Mondello1, 2
1SCIFAR, University of Messina, Messina, Italy;
2C.I.R., University Campus Bio-Medico
of Rome, Rome, Italy
P-247-W
A Highly Polar Ionic Liquid Stationary Phase for the Determination of Fatty Acid
Profile of Milk Lipid Fraction Carla Ragonese
1; Danilo Sciarrone
1; Elisa Grasso
1; Peter Quinto Tranchida
1; Luigi
Mondello1, 2
1SCIFAR, University of Messina, Messina, Italy;
2C.I.R., University Campus Bio-Medico
of Rome, Rome, Italy
P-248-W
Multidimensonal Liquid-preparative Gas Chromatopgraphy (LC-GC-GC-GC-
prep) for the Collection of Minor Components from Complex Matrices Danilo Sciarrone
1; Sebastiano Pantò
1; Peter Quinto Tranchida
1; Luigi Mondello
1, 2
1SCIFAR, University of Messina, Messina, Italy;
2C.I.R., University Campus Bio-Medico
of Rome, Rome, Italy
P-249-T
Half the Column, Same Chromatogram: Trimming the GC Column for
Maintenance While Maintaining Critical Resolution Between PBDEs Jack Cochran; Michelle Misselwitz; Jason Thomas
Restek Corporation, Bellefonte, PA USA
135
P-250-W
Determination of the Potent Flavour Compound Rotundone in Grapes and Wine
using MDGC-MS and Membrane Assisted Solvent Extraction Tracey Siebert; Sheridan R. Barter
The Australian Wine Research Institute, Glen Osmond, Australia
P-251-T
Absolute Molecular Configuration Strategies Using Preparative Gas
Chromatography and Multidimensional Gas Chromatography with Spectroscopy Leesun Kim; Blagoj Mitrevski; Philip Marriott; Kellie Tuck
Monash University, Clayton, Australia
P-252-W
Studies on Preparation of Rice Bran Oil Methyl Ester (RBOME) as an Alternative
Source of Bio-Diesel: A Green Chemistry Approach Bhalchandra Vibhute; Rajabhau Khotpal; Anand Kulkarni; Vijay Karadbhajane
LIT , RTMNU, Nagpur, India
P-253-W
Characterization of Pyrolytic Bio-Oils of the Sawdusts of Eucaliptus (Hardwood)
and Picea abies (Softwood) Using Gas Chromatography with Mass Spectrometric
Detector
Isadora Torri1, Candice Faccini
2, Ville Paasikallio
3, Desyree Ribeiro
2, Vera Sacon
4, Elina
Bastos Caramão2, Anja Oasmaa
3, Claudia A. Zini
1
1 PGCIMAT e Instituto de Química - UFRGS, Bento Goncalves, Porto Alegre, Brazil;
2
Instituto de Química - UFRGS, Bento Goncalves, Porto Alegre, Brazil; 3 VTT- Technical
Research Centre of Finland, Finland; 4 VTT Brasil, Alameda Araguaia, Barueri, Brazil
136
Liquid Chromatography
P-255-T
Statistical Analysis in Enrichment of Total Whey Protein by Continuous Foam
Fractionation Method Goutam Mukhopadhyay
Research Scholar, Kolkata, India
P-256-W
HPLC Analysis on Separation of BSA from Dilute Solution Goutam Mukhopadhyay
Research Scholar, Kolkata, India
P-257-T
Monolithic Capillary Columns Based on Pentaerythritol Acrylates for Molecular
Size Separation of Synthetic and Natural Polymers Timur Ibragimov; Alexander Kurganov; Elena Victorova; Alexander Korolev;
Anastasiya Kanatieva
A.V.Topchiev Institute of Petrochemical Synthesis, Moscow, Russia
P-258-W
Silanol Quality Batch to Batch Variations’ Effect on Assay/Impurity Methods Jun Han; Lan Li; Sophie Wang; Andrew Clausen
Amgen Inc., Thousand Oaks, CA USA
P-259-T
Kinetics of a Co-flow Membrane Contactor for Liquid-Liquid Extraction Jonas Hereijgers
1, 2; Tom Breugelmans
1, 2; Deirdre Cabooter
3; Wim De Malsche
1
1Vrije Universiteit Brussel, Brussels, Belgium;
2Artesis University College, Antwerp,
Belgium; 3KULeuven, Leuven, Belgium
P-261-T
Application of Recent Developments in Commercial HPLC Technology to Teach
Liquid Chromatography in Large-Enrollment Undergraduate Laboratories Christopher Palmer; Earle Adams; Holly Thompson
University of Montana, Missoula, MT USA
P-262-W
Impact of Instrument Dispersion on Performance of HPLC Capillary Columns Wendy Roe; Richard Henry; Hillel Brandes
Supelco, a Member of the SIGMA ALDRICH Group, Bellefonte, PA USA
137
P-263-T
Nano-Liquid Chromatography Coupled with Micro Free-Flow Electrophoresis for
Multi-Dimensional Separations of Peptides Matthew Geiger
University of Minnesota, Minneapolis, MN USA
P-264-W
Characterization of Sample Preparation of Pharmaceutical Tablets and Capsules
Using Enhanced Fluidity Liquid Extraction Fadi Alkhateeb; Kevin Thurbide
University of Calgary, Calgary, AB Canada
P-265-T
A Thermospray Interface for Liquid Chromatography with Acoustic Flame
Detection Andrea Scott; Kevin Thurbide
University of Calgary, Calgary, AB Canada
P-266-W
Efficient On-line SPE-LC-MS Using a Molecularly Imprinted Adsorbent for
Determination of Sulpiride Kenta Kuroda; Takuya Kubo; Koji Otsuka
Kyoto University, Kyoto, Japan
P-268-W
Subcritical Water Extraction of Common Pharmaceuticals from Commercial
Formulations Jillian N. Murakami; Kevin B. Thurbide
University of Calgary, Calgary, AB Canada
P-269-W
Silica-based Monolithic Capillary Columns Modified by Liposomes for
Characterization of Analyte-liposome Interactions by Capillary Liquid
Chromatography Dana Moravcová
1; Josef Planeta
1; Susanne Wiedmer
2
1Institute of Analytical Chemistry of the ASCR, Brno, Czech;
2University of Helsinki,
Finland
P-270-W
Analysis of Synthetic Drugs Using Electron and Chemical Ionization High
Resolution Time-of-Flight Mass Spectrometry David E. Alonso; Joe Binkley
LECO Corporation, St. Joseph, MI USA
138
P-271-W
Electron Impact and Chemical Ionization High Resolution Time-of-Flight Mass
Spectrometry Analyses of Blood Plasma Samples David E Alonso; Jeff Patrick; Joe Binkley; John Heim
LECO Corporation, St. Joseph, MI USA
P-273-T
Continuous vs. Stop-Flow Online Approaches for Comprehensive Two-dimensional
Liquid Chromatography of Lipids Paola Donato
1, 2; Nermeen Fawzy
2; Francesco Cacciola
3, 4; Marco Beccaria
2; Luigi
Mondello1, 2
1C.I.R., University Campus Bio-Medico of Rome, Rome, Italy;
2SCIFAR, University of
Messina, Messina, Italy; 3 SASTAS, University of Messina, Messina, Italy;
4Chromaleont
s.r.l., Messina, Italy
P-274-T
Electron Impact Mass Spectra of Non vtolatile Compound Through a Nano LC-EI-
MS System Danilo Sciarrone
1; Francesca Rigano
1; Peter Quinto Tranchida
1; Luigi Mondello
1, 2
1SCIFAR, University of Messina, Messina, Italy;
2C.I.R., University Campus Bio-Medico
of Rome, Rome, Italy
139
Technical Seminars
Sponsored by LECO Corporation
Tuesday, May 14, 2013
12:00 – 13:00
Mojave Learning Center
Addressing Analytical Challenges Using High Performance Gas Chromatography
and Two-Dimensional Gas Chromatography
Jef Focant, University of Liége, Liége, Belgium
The utilization of high performance GC-TOFMS techniques—including fast GC,
GC×GC, and GC interfaced to high resolution mass spectrometry—continues to advance,
contributing to numerous fields of study. These areas include metabolomics,
petrochemical, food safety, environmental, and food/flavor/fragrance, among others. This
seminar will emphasize examples of these applications with a focus on comprehensive
two‐dimensional GC coupled to time‐of‐flight mass spectrometry (GC×GC‐TOFMS) as
one of the most efficient tools for complex sample analysis. Highlights include the latest
developments achieved when GC×GC-TOFMS is applied to the evaluation of breath
samples for the identification of a larger VOC profile to support non-invasive, early
detection of lung cancer by comprehensive exhaled breath analysis. Additionally,
information will be presented from LECO on recent technological advancements.
Notes:
140
Sponsored by Restek Corporation
Tuesday, May 14, 2013
12:00 – 13:00
Catalina Ballroom
Twice the Column, Better Separations, Same Analysis Time: Analysis of the EFSA
PAH4 with the New Rxi-PAH GC Column
Half the Column, Same Separation: Extending the Lifetime of a GC Column after
Column Trimming Maintenance with Method Translation
Jack Cochran, Amanda Rigdon, Roy Lautamo, Shawn Reese, Michelle Misselwitz;
Restek Corporation, Bellefonte, PA USA
Polycylic aromatic hydrocarbons (PAHs) are toxic (carcinogenic, mutagenic, teratogenic,
etc.) compounds that are often found in food. They require monitoring by capillary gas
chromatography with mass spectrometry (GC-MS), often at very low levels. Many of
these PAHs are isobaric, so MS is insufficient to quantify them in an unbiased fashion if
they coelute, which means they must be chromatographically separated prior to detection.
As defined by the European Food Safety Authority, the PAH4, benz[a]anthracene,
chrysene, benzo[b]fluoranthene, and benzo[a]pyrene, represent most of the toxicity for
PAHs found in food samples. Likely GC coelutions that would lead to qualitative and
quantitative bias for PAH4 include triphenylene and chrysene (m/z 228), benzo[b]
fluoranthene with benzo[k]fluoranthene and benzo[j]fluoranthene, and benzo[e]pyrene
and benzo[a]pyrene. The triphenylene and chrysene coelution is usually impossible to
resolve on most available GC stationary phases.
A new GC stationary phase has been developed that separates the PAH4, the PAH8, and
many more PAHs that can be present in both food and environmental samples.
Chromatograms that detail these separations will be shown, and column ruggedness and
thermal stability will be explored, in addition to showing how the column can be trimmed
multiple times for maintenance while still maintaining the necessary separations.
Column maintenance by trimming is a necessary activity when analyzing dirty samples,
but many GC users forget to enter the new length of the column in GC flow control
software and translate the GC oven program so that peak elution order and separations
can be maintained. This ultimately leads to premature disposal of a GC column that has
significant lifetime left in it. With simple, proper method translation a GC column can
perform very well, even after trimming to almost half its original length.
Notes:
141
Sponsored by Thermo Scientific
Tuesday, May 14, 2013
12:00 – 13:00
Madera Ballroom
Part 1: Advancements In Modern Chromatography Equipment Design To Do More
With Less
Terri Christison1; Massimo Santoro
2,
1Thermo Scientific, Sunnyvale, CA USA;
2Thermo
Scientific, Lombardy, Italy
Gas chromatographic equipments require specific hardware with appropriate inlets and
detectors selection based on the applications run. Changing a system configuration to
follow a new analytical need is a difficult operation and often results in a new system
requirement. This increases the overall capital investments, as well as the operational
budget costs encountered, such as expanded gas supplies, energy consumption, and
consumable usage, even when the GC are not in use.
A new approach to the GC instrumentation design that allows easy configuration change
and/or upgrade is illustrated. As in modern modular HPLC, the fundamental GC
components are independent systems combined to produce the desired analytical layout.
Inlets and detectors are modular devices incorporating all flow, pressure, temperature,
and signal controls then housed onto the GC oven.
This innovative approach enables users to efficiently adjust resources to meet new and
existing demands with fewer systems. In this seminar, we will illustrate some innovative
ways to reduce the total number of GC systems used to accomplish the same
productivity, share the existing components for maximum efficiency, and quickly
redistribute application workload as needed - all with minimal capital investment. We
will also show how instrument downtime for maintenance activities, whether planned or
unplanned, can basically be reduced to zero.
Details on the technological choices and implications determined by this approach will be
also discussed in this presentation.
Part 2: Capillary Ion Chromatography – Always On, Always Ready
Terri Christison1; Massimo Santoro
2,
1Thermo Scientific, Sunnyvale, CA USA;
2Thermo
Scientific, Lombardy, Italy
Ion chromatography (IC) with suppressed conductivity is a well established method
across multiple industries for the determinations of inorganic ions. These determinations
are necessary to meet regulatory requirements and to maintain product quality. The recent
products, high-pressure capable capillary IC systems and 4-m particle ion-exchange
columns, combine the advantages of a walk-up system with the highly efficient
separations possible on 4-m particle columns. With L/min flow rates and eluent
142
consumption as low as 15 mL/day, capillary IC systems can be operated 24/7. These true
walk-up systems have very low system noise with low operating costs, equilibration
times, and waste generation. The 4 m particle size columns are the latest advancement
in ion-exchange chromatography separations with theoretical plate counts up to 12,000 to
18,000/column. These smaller particles increase chromatographic resolution of critical
pairs and permit faster separations while maintaining excellent resolution. The high-
pressure capable capillary IC systems facilitate the use of these high-efficiency ion-
exchange columns to accommodate increased flow rates and higher operating back
pressures, often up to 3,000-4,500 psi. Here, I demonstrate the advantages of using 4 m
particle-size ion-exchange columns on high-pressure capillary IC systems for inorganic
ion determinations.
Notes:
143
Sponsored by Supelco, a Member of the SIGMA ALDRICH Group
Wednesday, May 15, 2013
12:00 – 13:00
Mojave Learning Center
TBD
Information not available at the time of print.
Notes:
144
Sponsored by Zoex Corpoartion
Wednesday, May 15, 2013
12:00 – 13:00
Catalina Ballroom
TBD
Information not available at the time of print.
Notes: