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
1
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 ......
2
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
3 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
4
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
5 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
6 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.
7 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
8 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
9 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.
10 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.
11 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
12 Monday, May 13, 2013
07:30 – 18:30 Registration in the Ballroom Foyer
Plenary Lecture in the Catalina and Madera Ballrooms Session Chairs: Jean-Marie Dimandja, Spelman College, Atlanta, GA USA and Philip Marriott, Monash University, Clayton, Australia
08:30 – 08:45 GC×GC Introduction, Welcome and Presentation of the GC×GC Scientific Achievement Award Jean-Marie Dimandja, Spelman College, Atlanta, GA USA Philip Marriott, Monash University, Clayton, Australia
08:45 – 09:15 (L-01-01) GC×GC: In Hot Pursuit of More Chemical Information Robert E. Synovec, University of Washington, Seattle, WA USA
09:15 – 9:30 Mini Break
Instrument Development in the Catalina and Madera Ballrooms Session Chairs: Jean-Marie Dimandja, Spelman College, Atlanta, GA USA and Philip Marriott, Monash University, Clayton, Australia
09:30 – 09:55 (L-01-02) Using a Simple Selectivity Model to Design Better GC×GC Separations John Seeley1; Abhijit Ghosh1; Stacy Seeley2, 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 Savareear1; Laura Tedone2; Robert Shellie1; 1ACROSS, University of Tasmania, Hobart Australia; 2University of Messina, Messina Italy
13
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 Peroni2; 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 Mondello1,2, 1SCIFAR, University of Messina, Messina, Italy; 2C.I.R., Campus Bio-Medico, Rome, Italy
12:40 – 13:00 (L-01-09) Use of Multidimensional Retention Normalization in Predictive GC×GC for Column Set Selection and Separation Optimization Jean-Marie Dimandja, Spelman College, Atlanta, GA USA
13:00 – 14:00 Lunch Break – Participants on their own
14:00 – 15:30 Poster Session – Visit the Exhibitors and Posters in the Foyer and Pasadena, Sierra and Ventura Ballroom
14 Monday, May 13, 2013 continued…
GC×GC Applications I in the Catalina and Madera Ballrooms Session Chairs: Debora Almeida Azevedo, Federal University, Rio de Janeiro, Brazil and Philip Marriott, Monash University, Clayton Australia
15:30 – 15:50 (L-01-10) GC×GC: The Importance of Second Dimension Column Length in Promoting True Peak Capacity Increase Comprehensive Two-Dimensional Gas Chromatography Jack Cochran1; Michelle Misselwitz1, Julie Kowalski1, 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 Manfroi2; Mauro Zanus3; Marcelo Lazzarotto3; Claudia Alcaraz Zini1, 1Instituto de Química;Porto Alegre, Brazil 2Instituto de Ciência e Tecnologia de Alimentos, Universidade Federal do Rio Grande do Sul, Porto Alegre, Brazil; 3Embrapa Uva e Vinho, Bento Gonçalves, Brazil
16:10 – 16:30 (L-01-12) Evaluation of GC - Online Reduction × GC for the Separation of Fatty Acid Methyl Esters Pierluigi Delmonte; Ali Reza Fardin Kia; Jeanne I. Rader, FDA, College Park, MD USA
16:30 – 16:50 (L-01-13) Extending the Orthogonality to the Whole Analytical Process: Does it Open New Perspectives in Flavoromics? Chiara Cordero; Cecilia Cagliero; Erica Liberto; Luca Nicolotti; Patrizia Rubiolo; Barbara Sgorbini; Carlo Bicchi, University of Turino, Turino, Italy
16:50 – 17:20 PM Break – Visit the Exhibitors and Posters in the Foyer and Pasadena, Sierra and Ventura Ballroom
15 Monday, May 13, 2013 continued…
GC×GC Applications II in the Catalina and Madera Ballrooms Session Chairs: Blagoj Mitrevski, Monash University, Clayton, Australia and Luigi Mondello, SCIFAR, University of Messina, Messina, Italy
17:20 – 17:40 (L-01-14) TD-GC×GC-TOFMS Study of Human Cadaveric VOC Profiles Pierre-Hugues Stefanuto1; Sonja Stadler2; Romain Pesesse1; Kayte Perrault3; Shari Forbe3s; Jean-Francois Focant1, 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 Cordero2; Carol Bicchi2; 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 Sandlin1; James Griffith1; Kefu Sun1; Jim Luong2; Rob Edam3; W. Christopher Siegler1; Patric Eckerle4, 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. Özel1; Noelia Ramirez1; Alastair C. Lewis2; Emanuela Finessi1; 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
16 Tuesday, May 14, 2013
08:00 – 17:20 Registration in the Ballroom Foyer
08:30 – 14:00 See ISCC Program for Schedule – Page 87
14:00 – 15:30 Poster Session – Visit the Exhibitors and Posters in the Foyer and Pasadena, Sierra and Ventura Ballroom
Phillips Award Lecture in the Catalina and Madera Ballrooms Session Chair: Jean-Marie Dimandja, Spelman College, Atlanta, GA USA
15:30 – 16:00 (L-02-06) Revolution of Hydrocarbons Analysis by Comprehensive Two- dimensional Gas Chromatography: The Never Ending Story Thomas Dutriez1; Ward D’Autry1; Jeroen Knooren1; Gerard Kwakkenbos1; John Mommers1,2, 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. Dimandja2; Jane E. Hill1; 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 Muscalu1; Karl Jobst1; Tony Chen1; Gerry Ladwig1; Li Shen1; Eric Reiner2; Dave Morse1, 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 Hoh1; Carlos Manzano2; Staci Massey Simonich2, 1San Diego State University, San Diego, CA USA; 2Oregon State Universiy, Corvallis, OR USA
17 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
18 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:
19 L-01-02
Using a Simple Selectivity Model to Design Better GC×GC Separations
John Seeley1; Abhijit Ghosh1; Stacy Seeley2
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:
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
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:
21 L-01-04
GC×2GC and 2GC×GC Using Contra-directional Thermal Modulation
Benjamin Savareear1; Laura Tedone2; Robert Shellie1
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:
22 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:
23 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:
24 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:
25 L-01-08
Gas Velocity at the Point of Re-Injection: An Additional Parameter in Comprehensive 2D GC Optimization
Peter Tranchida1; Luigi Mondello1, 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:
26 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.
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27 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 Misselwitz1; Julie Kowalski1; Mark Merrick2
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.
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28 L-01-11
Application of Comprehensive Two-Dimensional Gas Chromatography to the Analysis of Volatile Compounds of Brazilian Wines
Juliane E. Welke1; Marcelo Lazzarotto3; Vitor Manfroi2; Mauro Zanus3; Cláudia Zini1
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.
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29 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.
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30 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
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31 L-01-14
TD-GC×GC-TOFMS Study of Human Cadaveric VOC Profiles
Pierre-Hugues Stefanuto1; Sonja Stadler2; Romain Pesesse1; Kayte Perrault3; Shari Forbes3; Jean-Francois Focant1
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.
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32 L-01-15
Chemical Blueprint of Extra Virgin Olive Oil
Giorgia Purcaro1; Chiara Cordero2; Carlo Bicchi2; LanfrancoConte1
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.
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33 L-01-16
Advances in the Analysis of Olefin Monomers and Polymers by Comprehensive Two Dimensional Gas Chromatography (GC×GC)
William Winniford1; Anna Sandlin1; James Griffith1; Kefu Sun1; Jim Luong2; Rob Edam3; W. Christopher Siegler1; Patric Eckerle4
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.
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34 L-01-17
Development of Nitrogen Chemiluminescence as a Powerful Detector for GC×GC
Jacqueline Hamilton1; Mustafa Z. Özel1; Noelia Ramirez1; Alastair C. Lewis2; 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.
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35 L-02-06
Revolution of Hydrocarbons Analysis by Comprehensive Two-Dimensional Gas Chromatography: The Never Ending Story
Thomas Dutriez1; Ward D’Autry1; Jeroen Knooren1; Gerard Kwakkenbos1; 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.
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36 L-02-07
Identifying Biomarkers of P. aeruginosa Antibiotic Susceptibility Using GC×GC- TOFMS and Fisher Ratios
Heather Bean1; Jean-Marie D. Dimandja2; Jane E. Hill1
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.
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37 L-02-08
The Analysis of Halogenated Organics in Environmental Samples Using Comprehensive Two-Dimensional Gas Chromatography (GC×GC)
Alina Muscalu1; Karl Jobst1; Tony Chen1; Gerry Ladwig1; Li Shen1; Eric Reiner2; 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
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38 L-02-09
Simultaneous Analysis for Complex PAH Mixtures Using Novel Column Combinations in GC×GC/TOF-MS
Eunha Hoh1; Carlos Manzano2; Staci Massey Simonich2
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.
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39 L-02-10
Taking a Good Dose of High Separation Medication for Gas Chromatography Analysis of Fatty Acid Methyl Esters
Philip Marriott; Annie Zeng; Asia Nosheen; Yada Nolvachai; Blagoj Mitrevski; Sung- Tong Chin
Monash University, Clayton, Australia
Gas chromatography (GC) of fatty acid methyl esters (FAME) continues to exercise the intellect of analysts, and exact a toll from those who seek to achieve maximum resolution of this complex mixture of homologues, with their many isomeric variations. That FAME are of importance to a broad interest area of the chemical sciences is a given - including nutrition, plant and animal fats, cell constituents, and even in amniotic fluids. The classical challenge to accomplish high resolution separation often relies upon a combination of very (ultra-) long separation columns, and specialty (usually polar high cyano-propyl content, and more recently ionic liquid) phases. But there have been interesting and paradigm-confronting shifts in advances made in coupled column GC methodologies. Whilst the first demonstration of GC´GC analysis of FAME was conducted over 10 years ago, it seems that the message of the advantages of this approach was not broadly adopted - perhaps not surprisingly.
Our efforts in this task were first reported in 2002 (Lipids, 37 (2002) 715). Both polar - non-polar and non-polar - polar geometries were tested. In the meantime research developed approaches incorporating ionic liquid phases. We have recently re-visited this topic, and have also studied a range of ionic-liquid phases, integrated multidimensional gas chromatography and GC´GC methods, investigation of comparative performance of various highly-selective GC phases for typical FAME mixtures, and a range of plant oils, and soil bacterial FAME. The search for fast and effective FAME analysis continues.
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40 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 Ramírez1; Mustafa Z. Özel1; Rosa Maria Marcé2; Francesc Borrull2; Alastair C. Lewis3; Jacqueline F. Hamilton1 1University of York, York, United Kingdom; 2University Rovira i Virgili, Tarragona, Spain; 3NCAS, University of York, York, United Kingdom
41 Application of GC×GC to Smoke and Residues
P-103-M Use of GC×GC-MS in Discrimination of Accelerant Products in Forensic Cases – Practical Case Report Thierry Ducellier; Guillaume Cognon; Audrey Junker; Bertrand Frere French Gendarmerie (IRCGN), Rosny Sous Bois, France
P-107-M Identification of New Markers of Wood Smoke Exposures in Firefighters Using GC×GC-TOF-MS Brian McCarry1; Sujan Fernando1; Lorne Fell2; David Alonso2; Joe Binkley2 1Department of Chemistry & Chemical Biology, Hamilton, ON Canada; 2LECO Corporation, St. Joseph, MI USA
P-108-M Evaluation of Dispersive and Cartridge Solid Phase Extraction Cleanups for Multi- Residue Pesticides QuEChERS Extracts of Finished Tobacco with GC×GC-TOFMS Jack Cochran; Michelle Misselwitz; Julie Kowalski Restek Corporation, Bellefonte, PA USA
P-109-M Utilizing GC×GC - TOFMS to Improve the Data Quality for the Analysis of Fire Debris Kari Organtini; Jessica Westland; Frank Dorman The Pennsylvania State University, University Park, PA USA
P-114-T Analysis of Mainstream Tobacco Smoke by SPME-GC×GC-TOFMS Michal Brokl1; Louise Bishop2; Christopher Wright2; Chuan Liu2; Kevin McAdam2; Jean-Francois Focant1 1University of Liège, Liège, Belgium; 2British American Tobacco, Southampton, United Kingdom
42 Application of GC×GC to Essential Oils and Related Techniques
P-102-T Whole Oil Analysis Using Comprehensive Two-Dimensional Gas Chromatography Coupled to Time-of-Flight Mass Spectrometry: A Powerful Tool for Sulfur Speciation Bárbara Ávila1; Vinícius Pereira1; Alexandre Gomes2; Débora Azevedo1 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 Biernacka1; Waldemar Wardencki2; Jacek Namieśnik2; 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 Villiers1; Elizabeth Ntlhokwe1; Jochen Vestner2; Elizabeth Joubert3; Nina Muller3; Matthew Edwards4; Tadeusz Górecki4 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 Fix1, 2; Joe Binkley1, 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 Koning1; Martijn Brandt2; Herrald Steenbergen2; Hans-Gerd Janssen2, 3 1LECO Instrumente GmbH, Mönchengladbach, Germany; 2Unilever Research and Development, Vlaardingen, the Netherlands; 3University of Amsterdam, Amsterdam, The Netherlands
43 P-119-T Comparison of Volatile Profiles of Base Wines and their Corresponding Sparkling Wines Through Comprehensive Two-Dimensional Gas Chromatography Juliane Welke1; Vitor Manfroi3; Mauro Zanus4; Marcelo Lazzarotto2; Cláudia Zini1 1Instituto de Química, UFRGS, Porto Alegre, Brazil; 2EMBRAPA Florestas, Colombo, Brazil; 3Instituto de Ciência e Tecnol de Alimentos, UFRGS, Porto Alegre, Brazil; 4EMBRAPA Uva e Vinho, Bento Gonçalves, Brazil
P-136-M Improvement of Comprehensive Two-Dimensional Gas Chromatography Separations through Injection Port Backflushing Matthew Edwards; Julien Crepier; Tadeusz Górecki University of Waterloo, Waterloo, ON Canada
44 Application of GC×GC to Drug Analysis
P-120-T Discovery-Based Analyses of Wastewater Samples for Characterization of Drug Usage Dr. Frank Dorman; Adrienne Brockman The Pennsylvania State University, State College, PA USA
P-121-T Analysis of Marijuana Street Samples for Simultaneous Potency and Trace Organic Composition Using GC×GC-FID/ECD Frank Dorman1; Amanda Leffler1; Emily Ly1; Jack Cochran2; Julie Kowalski2 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 Silva1; Alessandro Casilli1; Samantha S. Barbosa1; Raphael S.F. Silva2; Monica C. Padilha1; Henrique Marcelo G. Pereira1; Francisco R. Aquino Neto1 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
45
Application of GC×GC to Petrochemical Analysis
P-101-T Evaluation of Two Sets of Columns for the Characterization of Bio-Oil of Sugar Cane Straw Using Comprehensive Two-dimensional Gas Chromatography Maria Elisabete Machado; Nathalia Kives; Marcelo Migliorini; Cláudia Zini; Elina Caramão Instituto de Química, UFRGS, Porto Alegre, Brazil
P-126-T Recent Enhancements in Petrochemical Qualitative-to-Quantitative Workflow; Employing GC×GC-TOF-MS for Rapid Method Development and Automated Translation to GC×GC-FID Analysis Nick Bukowski; Steve Smith; Laura McGregor; Kurt Thaxton; Alun Cole ALMSCO International, Llantrisant, United Kingdom
P-127-T Advanced Hydrocarbon Characterization of Diesel Fuels Derived from Wide Range of Feedstocks Rafal Gieleciak1; Craig Fairbridge1; William Cannella2 1Natural Resources Canada, CanmetENERGY, Devon, AB Canada; 2Chevron Corporation, Richmond, CA USA
P-128-T A Beneficial GC×GC-TOFMS Procedure for Environmental Forensic Fingerprinting Utilizing Structural Classifications to Differentiate Light Crude Oils John Heim; Joe Binkley; Liz Humston-Fulmer LECO Corporation, St. Joseph, MI USA
P-129-T Quality Control Measures for Robust GC×GC-SCD Analysis for Petroleum Applications Jonathan Pierson; Wayne Rathbun; Paul Adams; Hung Pham UOP, Des Plaines, IL USA
P-130-T GC×GC as an Efficient Tool for High Throughput Tests in the Petroleum Industry: A Case Study Vincent Souchon1; Mélinda Tébib1; Noémie Caillol1; Frédéric Feugnet2 1IFPEN - Physics and Analysis Division, Solaize, France; 2IFPEN - Process Design Division, Solaize, France
46 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. Tessarolo1; Andrea Pinho2; Alessandro Casilli1; Débora A. Azevedo1 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 Silva1; Alessandro Casilli2; Gilberto Alves Romeiro1; 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
47
GC×GC Theory and Modulation Studies
P-135-M Development, Optimization and Applications of a Consumable-Free Thermal Modulator for Comprehensive Two-Dimensional Gas Chromatography Matthew Edwards; Tadeusz Górecki University of Waterloo, Waterloo, ON Canada
P-137-M High Speed Deans Switch for Comprehensive Two Dimensional Gas Chromatography Abhijit Ghosh1; Carly T. Bates 1; Stacy K. Seeley2; John V. Seeley1 1Oakland University, Rochester, MI USA; 2Kettering University, Flint, MI USA
P-139-M A Pooled Sample Approach in Ethanol Fed Mice by GC×GC-TOFMS Utilizing Standardized Methods and a Reference Feature for Biomarker Screening John Heim; David Alonso; Joe Binkley LECO Corporation, St. Joseph, MI USA
P-140-M Integrating GC×GC, (Ultra)High Resolution Mass Spectrometry and Mass Defect Analysis for the Identification of Halogenated Contaminants in the Environment Karl J Jobst; Vince Y Taguchi; Trudy Watson-Leung; Dave Poirier; Paul A. Helm; Eric J Reiner Ministry of the Environment, Toronto, ON Canada
P-141-M Sample Preparation, Comprehensive Two-Dimensional Gas Chromatography and Customized Data Mining for Biomarker Investigation in Geochemical Samples - a Case Study Elaine Marotta; Alessandro Casilli; Maria Regina Loureiro; Débora Azevedo; Francisco Aquino Neto LAGOA-LADETEC, Instituto de Química, UFRJ, Rio de Janeiro, Brazil
P-142-M Temperature-Tunable Selectivity in Comprehensive Two-dimensional Gas Chromatography John Mommers1, 2; Thomas Dutriez1; Giulia Pluimakers3; Jeroen Knooren1; Sjoerd van der Wal1, 2 1DSM Resolve, Geleen, The Netherlands; 2University of Amsterdam, Amsterdam, The Netherlands; 3Avans Hogeschool, Hertogenbosch, The Netherlands
48 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 Onodera1; Masaaki Ubukata2; John Dane2; Akihiko Kusai1 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 Röhler1, 2; Roland Kallenborn1, 3; Martin Schlabach2 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 Franchina1; Mariosimone Zoccali1; Peter Tranchida1; Luigi Mondello1, 2 1SCIFAR, University of Messina, Messina, Italy; 2C.I.R., University Campus-Biomedico, Rome, Italy
49
P-149-M Applications of GC×GC-High Resolution TOFMS Coupled with the Classical Soft Ionization Technique “Field Ionization” Masaaki Ubukata1; John Dane1; Robert B. Cody1; Jun Onodera2; Keisuke Ishii2; 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
50
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 Salivo1; Peter Tranchida1; Carla Ragonese1; Marco Beccaria1; Luigi Mondello1, 2 1SCIFAR, University of Messina, Messina, Italy; 2C.I.R., University Campus-Biomedico, Rome, Italy
P-124-M Qualitative and Quantitative Chemical Characterization of Volatile Organic Compunds in Indoor Air Environment by Different Chromtographic Techniques: GC×GC-TOFMS, GC-MS, GC-FID Joseane Ames1; Alessandro Casilli1; Adriana Gioda2; Débora Almeida Azevedo1 1Universidade Federal do Rio de Janeiro, Rio De Janeiro, Brazil; 2Pontifícia Universidade Católica do Rio de Janeiro, Rio de Janeiro, Brazil
51 ISCC 2013 Scientific Program Summary
Tuesday, May 14, 2013
08:00 – 17:20 Registration in the Ballroom Foyer
08:30 – 08:45 ISCC Introduction and Welcome Frantisek Svec, Lawrence Berkeley National Laboratories, Berkeley, CA USA
Golay Award Plenary Lecture in Catalina and Madera Ballrooms Session Chairs: Milos Novotny, Indiana University, Bloomington, IN USA and Andrew Tipler, PerkinElmer, Shelton, CT USA
08:45 – 09:30 (L-02-01) From Packed LC-columns via SFC to Open Tubular LC- columns Tyge Greibrokk, University of Oslo, Oslo, Norway
Plenary Lecture in Catalina and Madera Ballrooms Session Chair: James Jorgenson, University of North Carolina, Chapel Hill, NC USA
09:30 – 10:00 (L-02-02) Comprehensive 2D Chromatography: A Key to Unlock Closed Analytical Doors Luigi Mondello, SCIFAR, University of Messina, Messina, Italy
10:00 – 10:30 AM Break – Visit the Exhibitors and Posters in the Foyer and Pasadena, Sierra and Ventura Ballrooms
10:30 – 11:00 (L-02-03) Ionic Liquids in GC for Water Analysis and for LC-MS of Trace Anions Dan Armstrong, University of Texas at Arlington, Arlington, TX USA
11:00 – 11:30 (L-02-04) Ordered Monolithic Structures as Stationary Phases for Capillary Chromatography Emily Hilder; Dario Arrua; Paul Haddad; Katharina Dihm, ACROSS, University of Tasmania, Hobart, Australia
52 Tuesday, May 14, 2013 continued…
11:30 – 12:00 (L-02-05) Transport of Single DNA Molecules through Nanofluidic Channels Laurent Menard; Jinsheng Zhou; J. Michael Ramsey, University of North Carolina, Chapel Hill, NC USA
12:00 – 13:00 Technical Seminars
Addressing Analytical Challenges Using High Performance Gas Chromatography and Two-Dimensional Gas Chromatography Jef Focant, University of Liége, Liége, Belgium
Sponsored by LECO Corporation Mojave Learning Center
Twice the Column, Better Separations, Same Analysis Time: Analysis of the EFSA PAH4 with the New Rxi-PAH GC Column
Half the Column, Same Separation: Extending the Lifetime of a GC Column after Column Trimming Maintenance with Method Translation
Jack Cochran, Amanda Rigdon, Roy Lautamo, Shawn Reese, Michelle Misselwitz; Restek Corporation, Bellefonte, PA USA
Sponsored by Restek Corporation Catalina Ballroom
Part 1: Advancements In Modern Chromatography Equipment Design To Do More With Less Terri Christison1; Massimo Santoro2, 1Thermo Scientific, Sunnyvale, CA USA; 2Thermo Scientific, Lombardy, Italy
Part 2: Capillary Ion Chromatography – Always On, Always Ready Terri Christison1; Massimo Santoro2, 1Thermo Scientific, Sunnyvale, CA USA; 2Thermo Scientific, Lombardy, Italy
Sponsored by Thermo Scientific Madera Ballroom
13:00 – 14:00 Lunch – Participants on their own
14:00 – 15:30 Poster Session – Visit the Exhibitors and Posters in the Foyer and Pasadena, Sierra and Ventura Ballrooms
53 Tuesday, May 14, 2013 continued…
Microfluidics Session in the Mojave Learning Center Session Chairs: Will Black, University of North Carolina, Chapel Hill, NC USA and Susanne Wiedmer, University of Helsinki, Helsinki, Finland
15:30 – 15:55 (L-02-11) Automation of Cell Synchronization and Analysis on Microfluidic Devices Stephen Jacobson; Seth Madren; Michelle Hoffman; Pamela Brown; David Kysela; Yves Brun, Indiana University, Bloomington, IN USA
15:55 – 16:20 (L-02-12) Size-Selective Protein Fractionation in Arrays of Nanofluidic Channels Adam Woolley; Suresh Kumar; Jie Xuan; Aaron Hawkins; Milton Lee; Brigham Young University, Provo, UT USA
16:20 – 16:40 (L-02-13) Dielectrophoresis Applied to Biomolecule Manipulation and Nanocrystal Sorting Alexandra Ros, Arizona State University, Tempe, AZ USA
16:40 – 17:00 (L-02-14) Microchip Based Methods for Monitoring Nitric Oxide Metabolites in Single Cells and Freely Roaming Animals Susan Lunte, University of Kansas, Lawrence, KS USA
17:00 – 17:20 (L-02-15) Integrated Microfluidic Devices for Monitoring Nitric Oxide Production in Single Cells Eve C. Metto; Dulan B. Gunasekara; Susan M. Lunte; Christopher T. Culbertson, Kansas State University, Manhattan, KS USA
17:30 – 19:00 Exhibitor Reception – Visit the Exhibitors in the Ballroom Foyer
54 Wednesday, May 15, 2013
07:30 – 08:30 Meet the Expert – Students and Postdoc Only in the Ballroom Courtyard
08:00 – 18:00 Registration in the Ballroom Foyer
Instrumentation Development in the Catalina and Madera Ballrooms Session Chair: Mark Libardoni, Southwest Research Institute, San Antonio, TX USA and Jim Luong, Dow Chemical Canada, Fort Saskatchewan, AB Canada
08:30 – 08:55 (L-03-01) Ultra-fast, High Mass-resolution Multi-Reflection-Time-of- Flight-Mass Spectrometer as Detector for One-dimensional and Comprehensive Two-Dimensional Gas Chromatography: Characterization of Highly Complex Mixtures Ralf Zimmermann1; Thomas Gröger1; Marie Schäffer1; Benedikt Weggler1; Jürgen Wendt2; Martin Sklorz1; Theo Schwemer1, 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
55 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 Vos2; Laura Quinn2; Claudine Roos3; Rialet Pieters3; Egmont Rohwer4; John Giesy5,6,7,8; Henk Bouwman3, 1LECO Africa (Pty) Ltd, Kempton Park, South Africa; 2National Metrology Insitute of South Africa, Pretoria, South Africa; 3North West University, Potchefstroom, South Africa; 4University of Pretoria, Pretoria, South Africa; 5University of Saskatchewan, Saskatoon, SK Canada; 6Michigan State University, East Lansing, MI, USA; 7King Saud University, Riyadh, Saudi Arabia; 8City University of Hong Kong, Kowloon, Hong Kong, China
10:00 – 10:30 AM Break – Visit the Exhibitors and Posters in the Foyer and Pasadena, Sierra and Ventura Ballroom
Column Technologies I in the Mojave Learning Center Session Chairs: Gert Desmet, Vrije Universitiet Brussel, Brussels Belgium and Fernando Maya Alejandro, Universitat de les Illes Balears, Palma de Mallorca, Spain
08:30 – 08:55 (L-03-05) New Macroporous UHPLC Silica Particles for Biomolecular Separations Milos V. Novotny, Benjamin F. Mann, Amanda K.P. Mann, Sara E. Skrabalak, Indiana University, Bloomington, IN USA
08:55 – 09:20 (L-03-06) New Polymeric Monoliths with Structure Optimized for Molecular Mass Separation of Polymers Alexander Kurganov; Anastasiya Kanatyeva, Institute of Petrochemical Synthesis, Moscow Russia
09:20 – 09:40 (L-03-07) Generating More than 100,000 Theoretical Plates with Less than 50 Bar in Liquid Chromatography with Porous Pillar Arrays Manly Callewaert1; Jeff Op De Beeck1; Heidi Ottevaere1; Han Gardeniers2; Gert Desmet1; Wim De Malsche1, 1Vrije Universiteit Brussel, Brussels Belgium; 2Mesa+ Institute of Nanotechnology, Enschede The Netherlands
56 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 Mori1; Kenichi Nakane1; Akira Kobayashi1; Ikuo Ueta2; Hayato Takeuchi1; Kiyokatsu Jinno1; Yoshihiro Saito1; 1Toyohashi University of Technology, Toyohashi, Japan; 2University of Yamanashi, Kofu, Japan
10:00 – 10:30 AM Break – Visit the Exhibitors and Posters in the Foyer and Pasadena, Sierra and Ventura Ballrooms
Applications of Gas Chromatography in the Catalina and Madera Ballrooms Session Chair: Kevin Thurbide, University of Calgary, Calgary, AB Canada
10:30 – 10:55 (L-03-09) Identification of Unknown Metabolites with Accurate Mass GC-Chemical Ionization QTOF Mass Spectrometry Oliver Fiehn; John Meissen; Takeuchi Kouhei; Sean Adams University of California, Davis, Davis, CA USA
10:55 – 11:20 (L-03-10) GC and GCMS for Solar System Geochemistry and Planetary Atmospheres – Past Missions to State-of-the-Art Instrument Development Mark Libardoni, Southwest Research Institute, San Antonio, TX USA
11:20 – 11:40 (L-03-11) Multidimensional GC Combined with Accurate Mass, Tandem Mass Spectrometry, and Element-specific Detection for Identification of Sulfur Compounds in Tobacco Smoke Nobuo Ochiai1; Kikuo Sasamoto1; Kazuhisa Mitsui2; Yuta Yoshimura2; Frank David3; Pat Sandara3, 1GERSTEL KK, Tokyo Japan; 2Japan Tobacco Inc., Kanagawa Japan; 3Research Institute of Chromatography, Kortrijk Belgium
57 Wednesday, May 15, 2013 continued…
11:40 – 12:00 (L-03-12) Multidimensional Gas Chromatography and Planar Microfluidics with Tandem Sulfur Chemiluminescence and Flame Ionization Detection for Sulfur Compounds Analysis Jim Luong1; Ronda Gras1; Robert Shellie2; Hernan Cortes2,3, 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 Koino1; Hiroya Ota1; Mami Oketani1; Takayuki Kawai2; Kenji Sueyoshi1; Takuya Kubo1; Fumihiko Kitagawa3; 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 Wiedmer1; Annika Railila1; Jana Lokajová2; Ashley Holding1; Alistair King1, 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 Solinova1; Dusan Koval1; Martine Poitevin2; Jean-Marc Busnel2; Gabriel Peltre2, 1Czech Academy of Science, Prague, Czech Republic; 2Ecole Super De Physique et Chimie Industrielles, Paris, France
58 Wednesday, May 15, 2013 continued…
12:00 – 13:00 Technical Seminars
TBD Sponsored by Supelco, A Member of the SIGMA-ALDRICH Group Mojave Learning Center
TBD Sponsored by Zoex Corporation Catalina Ballroom
13:00 – 14:00 Lunch – Participants on their own
14:00 – 15:30 Poster Session – Visit the Exhibitors and Posters in the Foyer and Pasadena, Sierra and Ventura Ballroom
Young Scientist - GC in the Catalina and Madera Ballrooms Session Chair: Robert E. Synovec, University of Washington, Seattle, WA USA
15:30 – 15:45 (L-03-17) Better Sniffing – A Story of High-Resolution Wine Aroma Analysis Sung-Tong Chin1; Graham Eyres2; Philip Marriott1, 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 Organtini1; Frank Dorman1; Mark Merrick2, 1The Pennsylvania State University, University Park, PA USA; 2LECO Corporation, St. Joseph, MI USA
59 Wednesday, May 15, 2013 continued…
16:30 – 16:45 (L-03-21) From the Olympics to the North Sea Gas Fields –Using GC×GC to Investigate Atmospheric Complexity Richard Lidster; Jacqueline Hamilton; Alastair Lewis; Rachel Holmes; James Lee; James Hopkins, The University of York, York, United Kingdom
Young Scientist - LC in the Mojave Learning Center Session Chairs: Milton Lee, Brigham Young University, Provo, UT USA and Mary Wirth, Purdue University, West Lafayette, IN USA
15:30 – 15:45 (L-03-23) Development of a 2D LC-CE-ESI Platform for Peptide Mapping Applications Will Black; J. Scott Mellors; J. Michael Ramsey, University of North Carolina, Chapel Hill, NC USA
15:45 – 16:00 (L-03-24) Packing and Characterization of High Aspect Ratio LC Columns in Capillaries and Microfluidic Devices James Grinias1; Martin Gilar2; James Jorgenson1, 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 Alejandro1; Frantisek Svec2; Victor Cerdá1, 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
60 Wednesday, May 15, 2013 continued…
17:00 – 18:00 Panel Discussions
Prospects of Microfluidics in Chemical Separations
Moderator: J. Michael Ramsey, University of North Carolina, NC USA
Panel: Stephen Jacobson, Indiana University, Bloomington, IN USA Alexandra Ros, Arizona State University, Tempe, AZ USA Adam Woolley, Brigham Young University, Provo, UT USA
Catalina and Madera Ballrooms
61 Thursday May 16, 2013
07:30 – 08:30 Meet the Expert – Students and Postdocs Only in the Ballroom Courtyard
08:00 – 16:30 Registration in the Ballroom Foyer
Gas Chromatography Technology in the Catalina and Madera Ballrooms Session Chair: Joshua Whiting, 3 Degrees of Separation, Inc., Dayton, OH USA
08:30 – 08:55 (L-04-01) Development of a New Capillary Column Format Utilizing Single Column and Parallel Column Array Geometries for Improved Separations Frank Dorman, Penn State University, University Park, PA USA
08:55 – 09:20 (L-04-02) Germania-Based Sol-Gel Materials in Separation Science Abdul Malik; Chengliang Jiang; Abdullah Alhendal; MinhPhuong Tran; Emre Seyyal, University of South Florida, Tampa, FL USA
09:20 – 09:40 (L-04-03) Practical Reduction of Analysis Time in GC and GC/MS Using Existing Instrumentation Jaap De Zeeuw; Jim Whitford, Restek Corporation, Middelburg, The Netherlands
09:40 – 10:00 (L-04-04) New Developments in Ionic Liquid GC Stationary Phases Leonard M. Sidisky; James L. Desorcie; Greg A. Baney; Gustavo Serrano; Daniel L. Shollenberger; Katherine K. Stenerson, Supelco, A Member of the SIGMA-ALDRICH Group, Bellefonte, PA USA
10:00 – 10:30 AM Break - Visit the Exhibitors and Posters in the Foyer and Pasadena, Sierra and Ventura Ballrooms
Column Technologies II in the Mojave Learning Center Session Chair: James Grinias, University of North Carolina, Chapel Hill, NC USA and John C. Vinci, University at Buffalo, Buffalo, NY USA
08:30 – 08:55 (L-04-05) Improving Efficiency in Monolithic Capillary Column Liquid Chromatography Pankaj Aggarwal; Kun Liu; Dennis Tolley; John Lawson; Milton Lee, Brigham Young University, Provo, UT USA
62 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 Hinterwirth2; Elisabeth Haller2; Wolfgang Lindner2, 1University of Tuebingen, Tuebingen, Germany; 2University of Vienna, Vienna, Austria
10:00 – 10:30 AM Break - Visit the Exhibitors and Posters in the Foyer and Pasadena, Sierra and Ventura Ballroom
Sampling/Chemistry in the Catalina and Madera Ballrooms Session Chair: G.A. Eiceman, New Mexico State University, Las Cruces, NM USA
10:30 – 10:55 (L-04-09) Particulate Matter Composition as a Measure of Residential Wood Stove Emissions: Analytical Methods and Measurements in Impacted Air Sheds Christopher Palmer; Brittany Busby; Megan Bergauf; Tony Ward, University of Montana, Missoula, MT USA
10:55 – 11:20 (L-04-10) The Discovery of Attribution Signatures for Chemical Threat Agents Carlos Fraga, Pacific Northwest National Laboratory, Richland, WA USA
11:20 – 11:40 (L-04-11) Chemical and Botanical Diversity Studied through Chromatographic Analysis of Tropical Plants Secondary Metabolites Elena Stashenko, Industrial University of Santander, Bucaramanga, Colombia
11:40 – 12:00 (L-04-12) Sulfur Response Characteristics of a Novel Multi-Flame Photometric Detector for GC Kevin Thurbide; Adrian Clark, University of Calgary, Calgary, AB Canada
63 Thursday May, 16, 2013 continued…
12:00 – 13:30 Lunch Break – Participants on their own
LC×LC in the Mojave Learning Center Session Chairs: Vaclav Kasicka, Academy of Sciences of the Czech Republic, Prague Czech Republic and Luigi Mondello, SCIFAR, University of Messina, Messina Italy
10:30 – 10:55 (L-04-13) Method Development of Two-dimension Liquid Chromatography and its Practicability in Separating Complex Samples Qin Yang; Xianzhe Shi; Shuangyuan Wang; Lizhen Qiao; Yuanhong Shan; Xin Lu; Guowang Xu, Dalian Institute of Chemical Physics, CAS, Dalian China
10:55 – 11:20 (L-04-14) High Peak Capacity Separations of Biologically-important Molecules by using 2D LC×UHPLC Paola Donato, Università Campus Bio-Medico, Rome Italy
11:20 – 11:40 (L-04-15) On-line Coupling of Size Exclusion Chromatography with Mixed-mode Liquid Chromatography for Comprehensive Profiling of Biopharmaceutical Drug Product Yan He; Olga Friese; Qian Wang; Laura Bass; Michael Jones, Pfizer, Inc. Chesterfield, MO USA
12:00 – 13:30 Lunch Break – Participants on their own
Microfab GC and GC×GC in the Catalina and Madera Ballrooms Session Chair: Carlos Fraga, PACIFIC NORTHWEST NATIONAL LABORATORY, Richland, WA USA
13:30 – 13:50 (L-04-17) A Portable Microfabricated GC×GC for Vapor Sampling and Analysis R.J. Simonson1; D.H. Read1; A.W. Staton1; J.J. Whiting2, 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
64 Thursday May, 16, 2013 continued…
14:10 – 14:30 (L-04-19) A Micro Discharge Device as a Low Power Universal Multi- Channel Detector for Portable and MEMS Gas Chromatographs Adam McBrady, Honeywell ACS, Plymouth, MN USA
14:30 – 14:45 Mini Break
Applications Liquid Chromatography in the Mojave Learning Center Session Chairs: Alexandros Lamprou, Lawrence Berkeley National Laboratory, Berkeley, CA USA and Guowang Xu, Dalian Institute of Chemical Physics, Dalian, China
13:30 – 13:50 (L-04-20) Microfluidic Western Blot Robert Kennedy, University of Michigan, Ann Arbor, MI USA
13:50 – 14:10 (L-04-21) Rapid Isolation of High Solute Amounts by Using an On-Line 4D Chromatographic System (Prep LC-GC-GC-GC) Danilo Sciarrone1; Sebastiano Panto1; Peter Quinto Tranchida1; 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
65 Thursday May, 16, 2013 continued…
15:15 – 15:45 (L-04-24) Packing Capillary LC Columns with Sub-2 Micron Particles: Everything I Know is Wrong James Jorgenson; Edward Franklin; Laura Blue; James Grinias, University of North Carolina, Chapel Hill, NC USA
15:45 – 16:15 (L-04-25) Capillary Electrophoresis for Deep and Accurate Bottom-Up Proteomics Norm Dovichi, University of Notre Dame, Notre Dame, IN USA
16:15 – 16:30 Announcements of Awards and Posters
16:30 – 16:40 Invitation to 2014 Luigi Mondello, SCIFAR, University of Messina, Messina, Italy
16:40 – 16:45 Closing Comments Robert E. Synovec, University of Washington, Seattle, WA USA
66 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
67 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.
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68 L-02-02
Comprehensive 2D Chromatography: A Key to Unlock Closed Analytical Doors
Luigi Mondello1, 2
1SCIFAR, University of Messina, Messina, Italy; 2C.I.R., University Campus Bio-Medico of Rome, Rome, Italy
Comprehensive chromatography (CC) experiments are usually carried out on two analytical columns, linked in series, and with an independent (orthogonal) selectivity. A transfer device (generically defined as modulator), positioned (somewhere) between the two dimensions, enables the isolation and re-injection of chromatography bands from the first to the second column, in a sequential manner throughout the analysis. Separations in the second dimension are usually carried out in a rapid manner, and ideally must end before the next re-injection step. Consequently, a CC analysis can be considered as nothing more than a stream of fast one-dimensional analyses, performed on the secondary column. The most appraised advantage of CC methods, over the one-dimensional counterparts, is the enhanced resolving power: in theory, the peak capacity (nc) becomes that of the primary column, multiplied by that of the second. The present oral contribution is focused on the analytical benefits of CC methods (i.e., 2D GC, 2D LC, etc.), which have been exploited and emphasized by a constantly increasing part of the chromatography community, in particular over the last twenty years. The power of CC methods, along with recent advances in mass spectrometry (MS), have enabled a much deeper insight into the true qualitative and quantitative composition of real-world samples. In fact, the unsuspected complex nature of a multitude of sample-types has been elucidated through the enhanced resolving power of such analytical approaches. Additionally, the outstanding selectivity and sensitivity of specific CC methodologies (in particular with MS detection) has made trace (ppb level), and ultra-trace (ppt level and lower) target analysis feasible, reducing the need for tedious sample preparation processes.
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69 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.
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70 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.
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71 L-02-05
Transport of Single DNA Molecules through Nanofluidic Channels
Laurent Menard; Jinsheng Zhou; J. Michael Ramsey
University of North Carolina, Chapel Hill, NC USA
Nanofluidic platforms have been established as valuable tools for single molecule studies of macromolecules. In particular, significant effort has been invested in the development of fabricated nanochannels and nanopores for single molecule analyses of DNA. This work has advanced the fundamental understanding of polymer behavior under confinement and promises to offer technological value in applications such as DNA sizing, mapping, epigenetic analysis, and sequencing. All of these applications rely on the ability to extend relatively large DNA molecules (>1000 bases) from the random coil observed in free solution into linearized conformations suitable for spatially resolved characterizations. Confinement of DNA molecules in nanochannels having critical dimensions (width and depth) less than ~100 nm is an effective method for achieving this spatial control. As the nanochannel dimensions decrease, the conformational degrees of freedom available to a confined DNA molecule are reduced, and linear extension and longitudinal spatial resolution increase. Fabricating nanochannels with critical dimensions below 30 nm remains a significant technological challenge. The simplest devices consist of single nanochannels or arrays of parallel nanochannels. These devices were used to study the dynamics of electrokinetically-driven transport of single DNA molecules through nanochannels. The DNA molecules were stained with an intercalating dye (YOYO-1, Invitrogen) and observed on an inverted fluorescence microscopy (Nikon TE-2000) using a 60X or 100X oil immersion objective lens. Images were recorded at 350-400 frames/s using an electron-multiplying CCD camera (Photometrics Cascade II). From images such as these, the mobility of DNA molecules under varying degrees of confinement and important intramolecular relaxation dynamics were determined. DNA transport in channels as small as 20 nm has been characterized.
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72 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.
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73 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).
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74 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.
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75 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
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76 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.
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77 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 Gröger1; Marie Schäffer1; Benedikt Weggler1; Jürgen Wendt2; Martin Sklorz1; Theo Schwemer1
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
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78 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.
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79 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.
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80 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 Vos2; Laura Quinn2; Claudine Roos3; Rialet Pieters3; Egmont Rohwer4; John Giesy5,6,7,8; Henk Bouwman3
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.
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81 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.
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82 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.
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83 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 Beeck1; Heidi Ottevaere1; Han Gardeniers2; Gert Desmet1; Wim De Malsche1, 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.
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84 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 Nakane1; Akira Kobayashi1; Ikuo Ueta2; Hayato Takeuchi1; Kiyokatsu Jinno1; Yoshihiro Saito1
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.
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85 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.
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86 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.
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87 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 Sasamoto1; Kazuhisa Mitsui2; Yuta Yoshimura2; Frank David3; 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.
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88 L-03-12
Multidimensional Gas Chromatography and Planar Microfluidics with Tandem Sulfur Chemiluminescence and Flame Ionization Detection for Sulfur Compounds Analysis
Jim Luong1; Ronda Gras1; Robert Shellie2; Hernan Cortes2, 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.
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89 L-03-13
Combination of On-Line Sample Concentration and Mass Spectrometric Detection in Microscale Eectrophoresis
Hiroshi Koino1; Hiroya Ota1; Mami Oketani1; Takayuki Kawai2; Kenji Sueyoshi1; Takuya Kubo1; Fumihiko Kitagawa3; Koji Otsuka1
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.
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90 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.
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91 L-03-15 Characterization of Phosphonium-based Ionic Liquids and Their use in Electrokinetic Capillary Chromatography
Susanne Wiedmer1; Annika Railila1; Jana Lokajová2; Ashley Holding1; Alistair King1
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.
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92 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 Solinova1; Dusan Koval1; Martine Poitevin2; Jean-Marc Busnel2; Gabriel Peltre2
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:
93 L-03-17
Better Sniffing – A Story of High-Resolution Wine Aroma Analysis
Sung-Tong Chin1; Graham Eyres2; Philip Marriott1
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.
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94 L-03-18
User-friendly Method for GC×GC Optimization
Pierre-Hugues Stefanuto1; Jean-Marie Dimandja2; Jean-François Focant1
1University of Liège, Liège, Belgium; 2Spelman College, Atlanta, USA
Almost 30 years are gone since the first paper about multidimensional GC was published by John B. Phillips 1. After several years of developing process, Comprehensive Two Dimensional Gas Chromatography systems are in the commercialization step of its live time. During this period, the advantages of GC×GC, regarding to classical D1 system, were clearly demonstrated 2. However, the new parameters involve in a GC×GC method are still not completely understand and people don’t use it at the maximum of its capacity. According to the literature more and more group are using GC×GC for different kind of applications. Unfortunately, the orthogonality and the column set are most of the time poorly optimized. In this study, we develop an user-friendly method to choose the best column combination and the best separation parameters for a particular application. All these developments were based on different mix of standard call the Century mix and the Dimandja mix. These are the descendants of the Phillips mix create in 2003 by J. Dimandja 3.
This method is based on the Retention Index obtained in a classical GC analysis and projected in the 2D space. Using this projection method, we identified four major types of orthogonality based on the peak dispersion obtained. We name those: Normal, Reverse, Hybrid and Transpose orthogonality. To characterize these observations, we developed the Orthogonality Index. Going back to the mathematical definition of orthogonality, this factor is the angle formed between the alkane line and the aromatic hydrocarbon line in the chromatographic space. Using this predictive tool, people should be able to choose the best column set and to optimize easily the separation parameters.
1. Phillips, J.B. et al. Anal. Chem. 57, 2779-2787 (1985). 2. Dimandja, J.-M.D. Anal. Chem. 76, 167A-174A (2004). 3. Dimandja, J.-M D. et al. J Chromatogr a 1019, 261-272 (2003).
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95 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.
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96 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 Dorman1; Mark Merrick2
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.
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97 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.
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98 L-03-23
Development of a 2D LC-CE-ESI Platform for Peptide Mapping Applications
Will Black; J. Scott Mellors; J. Michael Ramsey
University of North Carolina, Chapel Hill, NC USA
The analysis of biological samples is becoming increasingly sophisticated as researchers from a variety of disciplines seek to simultaneously characterize numerous analytes at the molecular level. The continued expansion of proteomics, metabolomics, and many other - omics applications serves as a salient example of this trend. Increasing the scope of biological research necessitates improvements to existing separations methods, which are quickly becoming a bottleneck in sample analysis. One promising method for dramatically increasing separation performance is to perform multi-dimensional separations, e.g., coupling orthogonal separation methods sequentially to perform 2D in time separations. The serial coupling of separation methods is also attractive in situations where a single detector is desirable such as electrospray ionization. Previously, our laboratory has reported a two-dimensional separation platform based on coupling capillary liquid chromatography (LC) with microchip capillary electrophoresis- electrospray ionization (CE-ESI). We demonstrated the peptide mapping capabilities of this method by characterizing glycopeptides from a monoclonal antibody digest. This presentation will focus on the continued development of this technology by improving the sample transfer between the two dimensions and by incorporating new data analysis software. The sensitivity of this method can be greatly enhanced by increasing the percentage of the LC effluent that reaches the CE separation channel. The integration of a sample-focusing step between the LC and CE dimensions improves sample transfer by at least an order of magnitude, resulting in a significant increase in sensitivity. Furthermore, the utilization of better data analysis software improves the utility of this method by generating two-dimensional maps with simultaneous access to mass spectrometry data.
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99 L-03-24
Packing and Characterization of High Aspect Ratio LC Columns in Capillaries and Microfluidic Devices
James Grinias1; Martin Gilar2; James Jorgenson1
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.
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100 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.
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101 L-03-26
“Knitting” Poly(Styrene-divinylbenzene) Capillary Monoliths with Large Surface Area via Friedel-Crafts Slkylation with External Crosslinkers
Fernando Maya Alejandro1; Frantisek Svec2; Víctor Cerdà1
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.
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102 L-03-27
Development of a Capillary Column Coated with C60-Fullerene for Liquid Chromatographic Separations
Yoshiki Murakami; Takuya Kubo; Koji Otsuka
Kyoto University, Kyoto, Japan
Recently, carbon-based nanomaterials (e.g., graphene, fullerene, and carbon nanotubes) have been investigated in many fields because of their excellent properties. They have large delocalized π-electrons, which can form π-stacking interactions with aromatic compounds. Therefore the carbon nanomaterials have been studied for various applications in separation chemistry as adsorbents of solid-phase extraction and pseudostationary phases in electrokinatic chromatography.
As one of drawbacks of carbon-based nanomaterials, the aggregation via strong π- stacking interactions is troublesome, so they hardly dissolve and/or disperse in any solvents. This is the major limitation of carbon nanomaterials for a practical use. Though functionalizations of the surface of the carbon nanomaterials to improve its solubility have been studied, it varies the superficial properties of the materials. The aim of this study is to develop a novel separation medium in a capillary enabling a specific separation based on π-stacking using carbon nanomaterials by immobilizing the carbon nanomaterials onto the capillary inner wall for open-tubular capillary liquid chromatography (OT-CLC).
C60-fullerene was employed as a stationary phase because of its better solubility and reactivity compared to the other carbon nanomaterials. Perfluorophenyl azide (PFPA) as a photoactive molecule was used to immobilize the C60-fullerene onto the capillary inner wall. The conditions of immobilization of C60-fullerene were optimized and the capillaries were evaluated by OT-CLC. As a result, benzene was retained on the coated capillary while the other control columns showed no retention ability for benzene. These suggested that C60-fullerene was successfully immobilized onto the capillary inner wall. To evaluate the major interaction on the column, we analyzed both the coated capillary and a commonly used C18 column by comparison of the separation behaviors of alkylbenzenes and polycyclic aromatic hydrocarbons. The results suggested that π- stacking by the C60-fullerene effected the separation on the coated capillary.
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103 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.
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104 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.
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105 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.
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106 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.
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107 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.
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108 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.
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109 L-04-07
Nanoparticle-Based Sample Preparation for Biomarker Analysis by HPLC-MS/MS
Michael Lämmerhofer1, Helmut Hinterwirth2, Elisabeth Haller2, Wolfgang Lindner2
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.
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110 L-04-09
Particulate Matter Composition as a Measure of Residential Wood Stove Emissions: Analytical Methods and Measurements in Impacted Air Sheds
Christopher Palmer; Brittany Busby; Megan Bergauf; Tony Ward
University of Montana, Missoula, MT USA
Exposure to particulate matter (PM) and vapor phase chemical contaminants from biomass combustion in residential settings is a significant and emerging world health issue. It is estimated that one-half of the worlds households continue to cook and/or heat with solid biomass fuels and that 3% of global disease can be attributed to exposures resulting from this. There are some 8.9 million wood stoves in use in the US, with an average annual usage per heater of 2100 hours. Eighty to 90% of the wood stoves currently in use are old and inefficient, resulting in high levels of emissions.
Gas chromatography-mass spectrometry methods have been adapted and implemented for the analysis of several major components of wood smoke in ambient particulate matter. Special emphasis has been placed on quality control both in sampling and analysis. The results reaffirm that levoglucosan is a useful chemical marker of wood smoke particulate, and may present a relatively inexpensive alternative for quantitative apportionment of the contribution of biomass burning to overall PM levels. Application of the methods to the analysis of ambient air in communities where air quality is impacted by the use of residential wood stoves leads to a greater understanding of the source of the PM and the effectiveness of efforts to reduce PM levels. Application to the analysis of indoor air in homes utilizing wood stoves shows very high levels of wood smoke particulate in the homes, and dramatic reductions in the levels of particulate after wood stoves are replaced.
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111 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.
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112 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.
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113 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.
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114 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.
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115 L-04-14
High Peak Capacity Separations of Biologically-Important Molecules by Using 2DLCxUHPLC
Paola Donato1, 2; Francesco Cacciola3, 4; Paola Dugo1, 2; Luigi Mondello1, 2
1C.I.R., University Campus Bio-Medico of Rome, Rome, Italy; 2SCIFAR, University of Messina, Messina, Italy; 3SASTAS, University of Messina, Messina, Italy; 4Chromaleont s.r.l., Messina, Italy
The high complexity of many natural samples, especially foodstuffs, often overwhelms the separation capability of any one-dimensional LC techniques, given the high number of compounds that may be found, with high degree of structural similarity. In such situations, co-elutions are likely to occur, rendering detection difficult and quantification hampered. The employment of multidimensional chromatographic techniques may represent a viable tool in order to improve both peak capacity and the identification power, especially in the “comprehensive” (LCxLC) mode, in which the entire analyte sample is subjected to the “2D advantage”. Although posing more stringent requirements, the combination of normal-phase (NP) and reversed phase (RP) represents one of the most orthogonal approaches, maximizing the peak capacity of a 2D separation system. On the other hand, the use of RP in both dimensions alleviates technical challenges, while orthogonality can be tuned by different stationary phase selectivity and mobile phase composition. Enhanced separation power can be exploited through the serial coupling of more LC columns, under UHPLC conditions or using elevated temperatures. Whenever the high sample complexity requires high separation power in 2D, the stop-flow operation mode may be convenient over the continuous one. Selected applications for the analysis of bioactive molecules in foodstuffs are illustrated, and the instrumental/software aspects involved in the development of LCxLC techniques discussed.
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116 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.
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117 L-04-17
A Portable Microfabricated GC×GC for Vapor Sampling and Analysis
R. J. Simonson1; D.H. Read1; A.W. Staton1; J.J. Whiting2
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.
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118 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.
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119 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.
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120 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.
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121 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 Pantò1; Peter Quinto Tranchida1; Paola Dugo1, 2; Luigi Mondello1, 2
1SCIFAR, University of Messina, Messina, Italy; 2University Campus Bio-Medico of Rome, Rome, Italy
The collection of nanalytes from natural sources is the goal of each preparative system. Although wide-bore columns (0.53 mm I.D.) are commonly used, providing an enhanced sample capacity, an excess of on-column sample amounts will result in skewed peaks and decreased resolution. On the other hand, the collection of pure components requires the injection of lower amounts in order to avoid coelutions on the wide-bore column; as a consequence, the collection of highly pure components, at the milligram level, requires an increased total collection time. A prep-MDGC system was successfully used for the collection of pure components ranging from 10 to 30% concentration, collected at the milligram level, to allow a further characterization by means of other techniques (NMR, vapor-phase IR, MS). The demands for the collection analytes at concentrations <10%, would consist in an increased sample injection volume, but this option could lead to the exceed the GC liner capacity. To improve the capability of the system, an on-line 4D chromatographic system (prep LC-GC-GC-GC) instrument was developed. Such a system enabled the injection of higher sample volumes, the reduction of collection times, while maintaining high levels of purity. The system consists of an LC pre-separation step, followed by the transfer of the isolated fraction(s), to a large volume injector in the first GC instrument, by means of an LC-GC syringe-based interface. An SLB-5ms - Supelcowax 10 - SLB-IL59 ionic liquid stationary phase (0.53 I.D.) combination was used in the three GC dimensions, in order to provide three distinct selectivities. A preparative station, connected at the 3rd GC column outlet, allowed the recondensation of pure components in a tube.
Acknowledgments The Project was funded by the “Italian Ministry for the University and Research (MIUR)” within the National Operative Project “Hi-Life Health Products from the industry of foods”. Project ID: PON01_01499.
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122 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.
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123 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:
124 L-04-24
Packing Capillary LC Columns with sub-2 micron Particles: Everything I Know is Wrong
James Jorgenson; Edward Franklin; Laura Blue; James Grinias
University of North Carolina, Chapel Hill, NC USA
If one contemplates increasing the operating pressures in ultra high pressure liquid chromatography (UHPLC) to the range of 1,000 to 4,000 bars, particles around 1 micron size should be close to optimum for separations of small molecules. Larger molecules such as peptides and proteins should benefit from even further reductions in particle size. Smaller diffusion coefficients of larger molecules decrease the optimum mobile phase velocity for a given particle size, resulting in lower required pressures. These lower pressures can be traded for the possibility of using smaller particles with these larger molecules. Particles of approximately 0.8 micron would be desirable for use with peptides, while particles as small as 0.5 micron could prove useful with proteins.
We have had success packing capillary columns with non-porous reversed phase particles as small as 0.9 microns. In the case of porous reversed phase particles, however, we have had good results with particles only as small as 1.5 microns. Attempts to pack 1 micron porous particles have resulted in columns of inferior performance. Our past efforts have focussed on identifying slurry solvents that are the most effective at eliminating particle aggregates and dispersing the particles as individuals. Methods for the slurry packing of micron-sized particles, and preparation and characterization of columns packed with these particles, will be described.
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125 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.
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126 Capillary Electrophoresis
P-201-T A Study on the Conversion of Methanol to Formaldehyde in the GC Injection Port Chee Leong Kee1; Min Yong Low1; Laura Ciolino2 1Health Sciences Authority, Singapore, Singapore; 2USFDA Forensic Chemistry Center, Cincinnati, OH USA
P-202-W Latex Nanoparticle Pseudo-Stationary Phases for Electrokinetic Chromatography: Versatile Chemistry Presents Opportunities for Improvements in Performance Christopher Palmer; Andre Umansky; Jesse Hyslop University of Montana, Missoula, MT USA
P-203-T Metabolic Profiling Analysis of Tissues Based on CE-TOF/MS Jun Zeng; Chunxiu Hu; Peiyuan Yin; Jieyu Zhao; Guowang Xu Dalian Institute of Chemical Physics, CAS, Dalian, China
P-204-W Determination of Dietary Omega-3 and Omega-6 Fatty Acids in Food by Capillary Electrophoresis Kingsley Donkor; Laiel Soliman; John Church; Bruno Cinel; Dipesh Prema Thompson Rivers University, Kamloops, BC, Canada
P-205-T Applicability of Capillaries CovalentlyBound with Phospholipid Vesicles to Open- Tubular Capillary Electrochromatography-Mass Spectrometry Heidi Tiala1; Marja-Liisa Riekkola1; Susanne Wiedmer2 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 Gunasekara1; Pann Pichetsurnthorn1; Diogenes do Santos1, 2; Christopher Culbertson3; Susan Lunte1 1University of Kansas, Lawrence, KS USA; 2Federal University of Alagoas, Maceio, Brazil; 3Kansas State University, Manhattan, KS USA
127 P-207-T Sensitive Determination of Anions in Highly-Saline Oilfield Waters by Indirect Photometric Capillary Electrophoresis Kingsley Donkor1; Laiel Soliman1; Kenneth Schmidt2; John Crabtree3 1Thompson Rivers University, Kamloops, BC, Canada; 2Wilson Analytical Services Inc., Sherwood Park, AB, Canada; 3HJC Consulting Inc., Edmonton, AB, Canada
128 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 Santoro1; Sergio Guazzotti1; Danilo Pierone2; Alexandre Souza3; 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
129 P-216-W A New Column Optimized for Sulfur Selective Detection Allen Vickers1; Mitch Hastings1; LiYing Yu1; Gary Lee1; Jim Luong2; Ronda Gras2; Myron Hawryluk2 1Agilent Technologies, Folsom, CA USA; 2DOW Canada, Fort Saskachewan, AB, Canada
P-217-W PLOT Columns with Integrated Particle Trapping Yun Zou; Jan Peene; Allen Vickers; LiYing Yu; Gary Lee Agilent Technologies, Folsom, CA USA
P-218-T An Evaluation Ionic Liquid Capillary Columns for the FAME Isomer Analysis Leonard M. Sidisky; Greg A. Baney; Katherine K. Stenerson; Gustavo Serrano; James L. Desorcie; Daniel L. Shollenberger Supelco, a Member of the SIGMA ALDRICH Group, Bellefonte, PA USA
P-219-W Considerations for Choosing a Different Carrier Gas in Gas Chromatography Jaap De Zeeuw Restek Corporation, Middelburg, The Netherlands
P-220-W Deactivation of Metal Capillary Columns: Moving from Trace Sulfur Applications to Stable and Inert High Temperature GC Solutions Jaap De Zeeuw Restek Corporation, Middelburg, The Netherlands
P-221-T Application of High Retentive Porous Polymers in Miniaturized Systems for Analysis of Gases in Seconds Jim Whitford1, 2; Jaap De Zeeuw1, 2; Bill Bromps3; Chris van Tilburg4 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
130 P-223-W A “Pseudo”-Targeted Method Based on Gas Chromatography-quadrupole Mass Spectrometry for Plant Metabolic Profiling Investigation Yanni Zhao; Yanli Li; Yuwei Chang; Junjie Zhang; Chunxia Zhao; Xin Lu; Guowang Xu Dalian Institute of Chemical Physics, CAS, Dalian, China
P-224-T An Approach to Quantifying Petroleum Ether in Active Pharmaceutical Ingredients Jana Stavova; Curtis Tinker; Michelle Kubin; William Fish Bristol-Myers Squibb Company, New Brunswick, NJ USA
P-225-W Detection of Sildenafil Residues in Different Types of Gingseng Products with GC/MS Turgay Celik; Enis Macit; Ahmet Turan Isik; Hüsamettin Gul; Ahmet Turan Isik; K.Gökhan Ulusoy Gulhane Medical Faculty, Ankara, Turkey
P-226-T Sulfur Response in a Multiple Flame Photometric Detector Adrian Clark; Kevin Thurbide University of Calgary, Calgary, AB Canada
P-227-W Applications of High-Temperature GC - High-Resolution Time-of-Flight Mass Spectrometry in Food Analysis Sjaak de Koning1; Hans-Gerd Janssen2, 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 Spanik1; Olga Vyviurska1; Alexandra Pazitna1; Jelena Radonic2; Maja Turk- Sekulic2; Mirjana Vojinovic Miloradov2 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
131 P-230-T Characterization of Novel Materials for Microfluidic Gas Chromatography Ernest Darko; Kevin B. Thurbide University of Calgary, Calgary, AB Canada
P-231-W Comparison of Different Types of Vegetable Oils by GC×GC-TOFMS Olga Vyviurska; Nikoleta Jánošková; Ivan Špánik Institute of Analytical Chemistry, Bratislava, Slovakia
P-232-T GC Separation of Alkyl Esters of 2-CN, 2-BR Carboxylic Acid Enantiomers on 6- Tertbutyldimethysilyl-2,3-Di-Methyl (Ethyl, Propyl)-β- AND 6- Tertbutyldimethysilyl-2,3-Di-Ethyl-γ- Cyclodextrin Stationary Phases Darina Kačeriaková; Ivan Špánik Institue of Analytical Chemistry, Bratislava, Slovakia
P-233-W Identification of Unique Volatile Organic Compounds in Acacia Honey by GC×GC- TOF-MS Nikoleta Jánošková; Antónia Janáčová; Ivan Špánik Institute of Analytical Chemistry, Bratislava, Slovakia
P-234-T Flow Modulated Targeted Signal Enhancement forVolatile Organic Compounds Taylor Hayward; Ronda Gras; Jim Luong Dow Chemical Canada, Fort Saskatchewan, AB Canada
P-235-W Comparative Study of GC×GC-NCD and GC-IT-MS/MS for Determining Nicotine and Carcinogen Organic Nitrogen Compounds in Thirdhand Tobacco Smoke Noelia Ramírez1; Mustafa Özel1; Alastair Lewis2; Jacqueline Hamilton1; Rosa Maria Marcé3; Francesc Borrull3; Laura Vallecillos3 1University of York, York, United Kingdom; 2NCAS, The University of York, York, United Kingdom; 3Universitat Rovira i Virgili, Tarragona, Spain
P-236-T Analysis of Polymer Extracts by Gas Chromatography - High Resolution Time-Of- Flight Mass Spectrometry with Electron Impact and Chemical Ionization David E. Alonso; Joe Binkley LECO Corporation, St. Joseph, MI USA
132 P-237-W GC - TOFMS Analysis of Incurred Pesticides Found in Food Commodities Frank Dorman1; Ashley Gates1; Elizabeth Humston-Fulmer2; Chris Solloway1; Joe Binkley2; Jessica Westland1 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 Gras1; Jim Luong1, 2; Hernan Cortes2; Robert A. Shellie2 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 Gras1; Ronda Gras2; Taylor Hayward2; Jim Luong2 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 Cao1; Zhaoxia Liu1; Yun Zou2; Jan Peene2 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 Costa2; Karine Nicolli1; Cláudia Zini1; Vitor Manfroi2 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
133 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 Zoccali1; Flavio Franchina1; Simona Salivo1; Sebastiano Pantò1; Peter Tranchida1; Luigi Mondello1, 2 1SCIFAR, University of Messina, Messina, Italy; 2C.I.R., University Campus-Biomedico of Rome, Rome, Italy
P-246-W Combining Liquid Chromatography and Comprehensive Two-dimensional Gas Chromatography-Mass Spectrometry: A Powerful Approach for the Determination of Mineral Oil Food Contamination Danilo Sciarrone1; Mariosimone Zoccali1; Flavio Franchina1; Peter Quinto Tranchida1; Luigi Mondello1, 2 1SCIFAR, University of Messina, Messina, Italy; 2C.I.R., University Campus Bio-Medico of Rome, Rome, Italy
P-247-W A Highly Polar Ionic Liquid Stationary Phase for the Determination of Fatty Acid Profile of Milk Lipid Fraction Carla Ragonese1; Danilo Sciarrone1; Elisa Grasso1; Peter Quinto Tranchida1; Luigi Mondello1, 2 1SCIFAR, University of Messina, Messina, Italy; 2C.I.R., University Campus Bio-Medico of Rome, Rome, Italy
P-248-W Multidimensonal Liquid-preparative Gas Chromatopgraphy (LC-GC-GC-GC- prep) for the Collection of Minor Components from Complex Matrices Danilo Sciarrone1; Sebastiano Pantò1; Peter Quinto Tranchida1; Luigi Mondello1, 2 1SCIFAR, University of Messina, Messina, Italy; 2C.I.R., University Campus Bio-Medico of Rome, Rome, Italy
P-249-T Half the Column, Same Chromatogram: Trimming the GC Column for Maintenance While Maintaining Critical Resolution Between PBDEs Jack Cochran; Michelle Misselwitz; Jason Thomas Restek Corporation, Bellefonte, PA USA
134 P-250-W Determination of the Potent Flavour Compound Rotundone in Grapes and Wine using MDGC-MS and Membrane Assisted Solvent Extraction Tracey Siebert; Sheridan R. Barter The Australian Wine Research Institute, Glen Osmond, Australia
P-251-T Absolute Molecular Configuration Strategies Using Preparative Gas Chromatography and Multidimensional Gas Chromatography with Spectroscopy Leesun Kim; Blagoj Mitrevski; Philip Marriott; Kellie Tuck Monash University, Clayton, Australia
P-252-W Studies on Preparation of Rice Bran Oil Methyl Ester (RBOME) as an Alternative Source of Bio-Diesel: A Green Chemistry Approach Bhalchandra Vibhute; Rajabhau Khotpal; Anand Kulkarni; Vijay Karadbhajane LIT , RTMNU, Nagpur, India
P-253-W Characterization of Pyrolytic Bio-Oils of the Sawdusts of Eucaliptus (Hardwood) and Picea abies (Softwood) Using Gas Chromatography with Mass Spectrometric Detector Isadora Torri1, Candice Faccini2, Ville Paasikallio3, Desyree Ribeiro2, Vera Sacon4, Elina Bastos Caramão2, Anja Oasmaa3, Claudia A. Zini1 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
135 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 Hereijgers1, 2; Tom Breugelmans1, 2; Deirdre Cabooter3; Wim De Malsche1 1Vrije Universiteit Brussel, Brussels, Belgium; 2Artesis University College, Antwerp, Belgium; 3KULeuven, Leuven, Belgium
P-261-T Application of Recent Developments in Commercial HPLC Technology to Teach Liquid Chromatography in Large-Enrollment Undergraduate Laboratories Christopher Palmer; Earle Adams; Holly Thompson University of Montana, Missoula, MT USA
P-262-W Impact of Instrument Dispersion on Performance of HPLC Capillary Columns Wendy Roe; Richard Henry; Hillel Brandes Supelco, a Member of the SIGMA ALDRICH Group, Bellefonte, PA USA
136 P-263-T Nano-Liquid Chromatography Coupled with Micro Free-Flow Electrophoresis for Multi-Dimensional Separations of Peptides Matthew Geiger University of Minnesota, Minneapolis, MN USA
P-264-W Characterization of Sample Preparation of Pharmaceutical Tablets and Capsules Using Enhanced Fluidity Liquid Extraction Fadi Alkhateeb; Kevin Thurbide University of Calgary, Calgary, AB Canada
P-265-T A Thermospray Interface for Liquid Chromatography with Acoustic Flame Detection Andrea Scott; Kevin Thurbide University of Calgary, Calgary, AB Canada
P-266-W Efficient On-line SPE-LC-MS Using a Molecularly Imprinted Adsorbent for Determination of Sulpiride Kenta Kuroda; Takuya Kubo; Koji Otsuka Kyoto University, Kyoto, Japan
P-268-W Subcritical Water Extraction of Common Pharmaceuticals from Commercial Formulations Jillian N. Murakami; Kevin B. Thurbide University of Calgary, Calgary, AB Canada
P-269-W Silica-based Monolithic Capillary Columns Modified by Liposomes for Characterization of Analyte-liposome Interactions by Capillary Liquid Chromatography Dana Moravcová1; Josef Planeta1; Susanne Wiedmer2 1Institute of Analytical Chemistry of the ASCR, Brno, Czech; 2University of Helsinki, Finland
P-270-W Analysis of Synthetic Drugs Using Electron and Chemical Ionization High Resolution Time-of-Flight Mass Spectrometry David E. Alonso; Joe Binkley LECO Corporation, St. Joseph, MI USA
137 P-271-W Electron Impact and Chemical Ionization High Resolution Time-of-Flight Mass Spectrometry Analyses of Blood Plasma Samples David E Alonso; Jeff Patrick; Joe Binkley; John Heim LECO Corporation, St. Joseph, MI USA
P-273-T Continuous vs. Stop-Flow Online Approaches for Comprehensive Two-dimensional Liquid Chromatography of Lipids Paola Donato1, 2; Nermeen Fawzy2; Francesco Cacciola3, 4; Marco Beccaria2; Luigi Mondello1, 2 1C.I.R., University Campus Bio-Medico of Rome, Rome, Italy; 2SCIFAR, University of Messina, Messina, Italy; 3 SASTAS, University of Messina, Messina, Italy; 4Chromaleont s.r.l., Messina, Italy
P-274-T Electron Impact Mass Spectra of Non vtolatile Compound Through a Nano LC-EI- MS System Danilo Sciarrone1; Francesca Rigano1; Peter Quinto Tranchida1; Luigi Mondello1, 2 1SCIFAR, University of Messina, Messina, Italy; 2C.I.R., University Campus Bio-Medico of Rome, Rome, Italy
138 Technical Seminars
Sponsored by LECO Corporation
Tuesday, May 14, 2013 12:00 – 13:00 Mojave Learning Center
Addressing Analytical Challenges Using High Performance Gas Chromatography and Two-Dimensional Gas Chromatography Jef Focant, University of Liége, Liége, Belgium
The utilization of high performance GC-TOFMS techniques—including fast GC, GC×GC, and GC interfaced to high resolution mass spectrometry—continues to advance, contributing to numerous fields of study. These areas include metabolomics, petrochemical, food safety, environmental, and food/flavor/fragrance, among others. This seminar will emphasize examples of these applications with a focus on comprehensive two‐dimensional GC coupled to time‐of‐flight mass spectrometry (GC×GC‐TOFMS) as one of the most efficient tools for complex sample analysis. Highlights include the latest developments achieved when GC×GC-TOFMS is applied to the evaluation of breath samples for the identification of a larger VOC profile to support non-invasive, early detection of lung cancer by comprehensive exhaled breath analysis. Additionally, information will be presented from LECO on recent technological advancements.
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139 Sponsored by Restek Corporation
Tuesday, May 14, 2013 12:00 – 13:00 Catalina Ballroom
Twice the Column, Better Separations, Same Analysis Time: Analysis of the EFSA PAH4 with the New Rxi-PAH GC Column
Half the Column, Same Separation: Extending the Lifetime of a GC Column after Column Trimming Maintenance with Method Translation
Jack Cochran, Amanda Rigdon, Roy Lautamo, Shawn Reese, Michelle Misselwitz; Restek Corporation, Bellefonte, PA USA
Polycylic aromatic hydrocarbons (PAHs) are toxic (carcinogenic, mutagenic, teratogenic, etc.) compounds that are often found in food. They require monitoring by capillary gas chromatography with mass spectrometry (GC-MS), often at very low levels. Many of these PAHs are isobaric, so MS is insufficient to quantify them in an unbiased fashion if they coelute, which means they must be chromatographically separated prior to detection. As defined by the European Food Safety Authority, the PAH4, benz[a]anthracene, chrysene, benzo[b]fluoranthene, and benzo[a]pyrene, represent most of the toxicity for PAHs found in food samples. Likely GC coelutions that would lead to qualitative and quantitative bias for PAH4 include triphenylene and chrysene (m/z 228), benzo[b] fluoranthene with benzo[k]fluoranthene and benzo[j]fluoranthene, and benzo[e]pyrene and benzo[a]pyrene. The triphenylene and chrysene coelution is usually impossible to resolve on most available GC stationary phases.
A new GC stationary phase has been developed that separates the PAH4, the PAH8, and many more PAHs that can be present in both food and environmental samples. Chromatograms that detail these separations will be shown, and column ruggedness and thermal stability will be explored, in addition to showing how the column can be trimmed multiple times for maintenance while still maintaining the necessary separations.
Column maintenance by trimming is a necessary activity when analyzing dirty samples, but many GC users forget to enter the new length of the column in GC flow control software and translate the GC oven program so that peak elution order and separations can be maintained. This ultimately leads to premature disposal of a GC column that has significant lifetime left in it. With simple, proper method translation a GC column can perform very well, even after trimming to almost half its original length.
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140 Sponsored by Thermo Scientific
Tuesday, May 14, 2013 12:00 – 13:00 Madera Ballroom
Part 1: Advancements In Modern Chromatography Equipment Design To Do More With Less Terri Christison1; Massimo Santoro2, 1Thermo Scientific, Sunnyvale, CA USA; 2Thermo Scientific, Lombardy, Italy
Gas chromatographic equipments require specific hardware with appropriate inlets and detectors selection based on the applications run. Changing a system configuration to follow a new analytical need is a difficult operation and often results in a new system requirement. This increases the overall capital investments, as well as the operational budget costs encountered, such as expanded gas supplies, energy consumption, and consumable usage, even when the GC are not in use.
A new approach to the GC instrumentation design that allows easy configuration change and/or upgrade is illustrated. As in modern modular HPLC, the fundamental GC components are independent systems combined to produce the desired analytical layout. Inlets and detectors are modular devices incorporating all flow, pressure, temperature, and signal controls then housed onto the GC oven.
This innovative approach enables users to efficiently adjust resources to meet new and existing demands with fewer systems. In this seminar, we will illustrate some innovative ways to reduce the total number of GC systems used to accomplish the same productivity, share the existing components for maximum efficiency, and quickly redistribute application workload as needed - all with minimal capital investment. We will also show how instrument downtime for maintenance activities, whether planned or unplanned, can basically be reduced to zero.
Details on the technological choices and implications determined by this approach will be also discussed in this presentation.
Part 2: Capillary Ion Chromatography – Always On, Always Ready Terri Christison1; Massimo Santoro2, 1Thermo Scientific, Sunnyvale, CA USA; 2Thermo Scientific, Lombardy, Italy
Ion chromatography (IC) with suppressed conductivity is a well established method across multiple industries for the determinations of inorganic ions. These determinations are necessary to meet regulatory requirements and to maintain product quality. The recent products, high-pressure capable capillary IC systems and 4-m particle ion-exchange columns, combine the advantages of a walk-up system with the highly efficient separations possible on 4-m particle columns. With L/min flow rates and eluent
141 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.
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142 Sponsored by Supelco, a Member of the SIGMA ALDRICH Group
Wednesday, May 15, 2013 12:00 – 13:00 Mojave Learning Center
TBD
Information not available at the time of print.
Notes:
143 Sponsored by Zoex Corpoartion
Wednesday, May 15, 2013 12:00 – 13:00 Catalina Ballroom
TBD
Information not available at the time of print.
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144