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


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


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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


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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


08:30 – 14:00 See ISCC Program for Schedule – Page 87



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:

23

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:

24

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


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


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


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


2British American Tobacco, Southampton, United

Kingdom

43


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


45


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


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


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


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


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


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


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


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


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; 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



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


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


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;


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


2,


2Thermo


Sponsored by Thermo Scientific Madera Ballroom

13:00 – 14:00 Lunch – Participants on their own



54


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


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



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



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


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


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



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


60


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


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


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


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


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…


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


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


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


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


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


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


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


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


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


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;


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; Paola Dugo

1, 2; Luigi

Mondello1, 2


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


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


P-203-T

Metabolic Profiling Analysis of Tissues Based on CE-TOF/MS Jun Zeng; Chunxiu Hu; Peiyuan Yin; Jieyu Zhao; Guowang Xu


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


P-219-W

Considerations for Choosing a Different Carrier Gas in Gas Chromatography Jaap De Zeeuw


P-220-W

Deactivation of Metal Capillary Columns: Moving from Trace Sulfur Applications

to Stable and Inert High Temperature GC Solutions Jaap De Zeeuw


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


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


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


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


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


2C.I.R., University Campus-Biomedico


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;

Luigi Mondello1, 2




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; Luigi

Mondello1, 2




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; Luigi Mondello

1, 2




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


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


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


P-262-W

Impact of Instrument Dispersion on Performance of HPLC Capillary Columns Wendy Roe; Richard Henry; Hillel Brandes


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


P-265-T

A Thermospray Interface for Liquid Chromatography with Acoustic Flame

Detection Andrea Scott; Kevin Thurbide


P-266-W

Efficient On-line SPE-LC-MS Using a Molecularly Imprinted Adsorbent for

Determination of Sulpiride Kenta Kuroda; Takuya Kubo; Koji Otsuka


P-268-W

Subcritical Water Extraction of Common Pharmaceuticals from Commercial

Formulations Jillian N. Murakami; Kevin B. Thurbide


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


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


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;


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; Luigi Mondello

1, 2




139

Technical Seminars

Sponsored by LECO Corporation


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


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;


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


12:00 – 13:00

Madera Ballroom

Part 1: Advancements In Modern Chromatography Equipment Design To Do More

With Less


2,


2Thermo


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


2,


2Thermo


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


12:00 – 13:00

Mojave Learning Center

TBD

Information not available at the time of print.

Notes:

144

Sponsored by Zoex Corpoartion


12:00 – 13:00

Catalina Ballroom

TBD

Information not available at the time of print.

Notes:

37th International Symposium on Capillary Chromatography · Poster Information Poster Sessions Each...

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Transcript of 37th International Symposium on Capillary Chromatography · Poster Information Poster Sessions Each...