Day 2 :
Keynote Forum
Athula Attygalle
Center for Mass Spectrometry, Stevens Institute of Technology, USA
Keynote: Where is the charge located in multifunctional gaseous ions? A survey by Ion Mobility Mass Spectrometry
Time : 08:30- 08:55
Biography:
Athula Attygalle is a reaech professor at Stevens Institute of Technology, USA. After an international scientific safari (University of Ceylon, University of Sri Lanka, Tokyo Institute of Technology, University of Keele, University of Erlangen-Nürnberg, and University of Houston), Attygalle became the Director of the mass spectrometry facility of Cornell University in 1991, After 12 years at Cornell, Attygalle became a Professor at Stevens Institute of Technology in Hoboken, NJ, in 2001. He has published over 200 papers in reputed journals and holds five U.S. patents.
Abstract:
The preferred charge sites of protonated or deprotonated molecules in the gas phase has been a topic of extensive research. In fact, the exact location of the initial charge site of the precursor ion is requisite that should be addressed before any pragmatic interpretation of a fragmentation spectrum is attempted. Although the challenge appears seemingly simple, in reality it is not at all a trivial problem. One often assumes that the charge location can be easily predicted by knowing the gas-phase acidity or basicity of various groups present in a polyfunctional molecule. However, in reality this a very challenging problem because generalizations valid for solution-based chemistry cannot be extended directly to gas-phase phenomena. For example, there is sufficient experimental evidence to demonstrate that deprotonated p-hydroxybenzoic acid exists in gas phase as a mixture of carboxylate and phenoxide forms. Analogously, protonated aniline exists as mixture of nitrogen- or ring-protonated forms. Ion-mobility mass spectrometry (IM-MS) provides a way to determine relative population ratios of protomers or deprotomers that coexist under mass spectrometric ion generation conditions. Employing IM-MS separation, we demonstrate that mass spectrometric source conditions used for gas-phase ion generation play an important role on the relative ratios of isomeric protomers and deprotomers that coexist under a specific set of experimental conditions.
Keynote Forum
Eduard Rogatsky
Wadsworth Center, USA
Keynote: Root causes of LC/MS data variability
Time : 08:55- 09:20
Biography:
Prof. Rogatsky serves as the Editor-in-Chief for the Journal of Chromatography and Separation Techniques (OMICS publishing group). During the last 10 years (from 2005) he has published over 30 scientific papers in per-reviewed journals (mostly as the first author) and has presented over 50 posters and lectures. Overall, he has made more than a hundred scientific presentations and publications. Eduard completed his M.Sc. in physical chemistry at Belarus State University (former USSR) in 1990. He completed his PhD in bioanalytical chemistry (Bar-Ilan University, Israel) in 1998. At the end of 1999, he started his post-doctorate at Albert Einstein College of Medicine and became a faculty member since 2001 and was a mass spectrometry director at the Biomarker Analytical Resource Core. From October 2015 Dr. Rogatsky is a supervisor of the Chemical Threat Laboratory in the Division of Environmental Health Sciences at Wadsworth Center, Albany NY, USA and continue to be an Adjunct Professor at Albert Einstein College of Medicine.
Abstract:
In a past decade in a literature were addressed different methodological questions, related to data variability between immunoassays and LC/MS methods (during clinical assay standardizations studies). However, reasons of inter-lab proficiency testing variability, performed only on LC/MS instruments typically are not discussed. While a pipetations inaccuracy limit is typically within 3% interval, reported proficiency testing results produced by well validated LC/MS methods, could be exceeding 20% bias or ± 3S consensus interval, even if the same method and same instrument brand were used in other laboratories. I present case studies demonstrating impact of calibration curve design, instrument settings, LC and MS instrumental conditions and analyte source chemistry on test results of specimens, blanks and quality controls.
Keynote Forum
Jianmin Chen
Fudan University, China
Keynote: Tropospheric multiphase chemistry elevated by diverse mass-spectrometric techniques
Time : 09:20- 09:45
Biography:
Jianmin Chen has completed his PhD at the age of 29 years from Fudan University. He is an atmospheric Scientist, distinguished professor and directors of Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, and International Collaboration Base of Climate and Environment (Ministry of Science and Technology of China) at Fudan University. He was a visiting associate professor at University of Pittsburgh from 1996 to 1997, and regularly visiting scientist in Institut de Combustion Aérothermique, Réactivité et Environnement-CNRS. He has published more than 180 pre-reviewed papers in geoscience and chemistry journals such as Chem. Rev., J. Amer. Chem. Soc., Atmos. Chem. Phys., Environ Sci. Technol. and J. Geophy. Res., and serving as an associated editor of Sci. Total Environ., and board members of Aerosol Air Qual. Res., J. Environ. Sci. and Adv. Environ. Res.. He was honored as de chevalier dans l'ordre des palmes académiques, and the Enjoyment of the State Council of China special allowance in 2015.
Abstract:
Recently, multifarious mass-spectrometric techniques (MAF) have been rapidly developed and applied to tropospheric multiphase chemistry. They play an important role in the studies of secondary aerosol formation, chemical components, atmospheric oxidation, haze episodes and cloud condensation nuclei (CCN), which impact many aspects of air quality, health and global climate. Here, a variety of MST is introduced to investigate multiphase chemistry in ambient air and laboratory studies, (i) secondary organic aerosols (SOA) formation was investigated by single particle ToF mass spectrometry from α-pinene–ozone system with seed aerosols in an aerosol chamber; (ii) particulate nitrate formation was firstly explored by aerosol ToF mass spectrometry. High molecular weight species were observed in urban Shanghai aerosols; (iii) desorption electrospray ionization mass spectrometry has been applied for the first time to the analysis of SVOCs in atmospheric aerosols and only a 1 µL droplet sample is needed for analysis without or with little pretreatment; (vi) UHPLC coupled with Orbitrap MS was used in PM2.5 analysis. About 200 formulas of organosulfates, were found including dozens of formulas of nitrooxy- organosulfates with various numbers of isomers. It is increasing interest in MST combined with hygroscopic and optical techniques to explore atmospheric process and radiative forcing.
Keynote Forum
Ali Mohammad-Djafari
CNRS, France
Keynote: Inverse problems in Mass Spectrometry and Bayesian solutions
Biography:
Ali Mohammad-Djafari received the B.Sc. degree in electrical engineering from Polytechnic of Teheran, in 1975, the diploma degree (M.Sc.) from Ecole Supérieure d'Electricit(SUPELEC), Gif sur Yvette, France, in 1977, the "Docteur-Ingénieur" (Ph.D.) degree and "Doctorat d'Etat" in Physics, from the University of Paris Sud 11 (UPS), Orsay, France, respectively in 1981 and 1987.He was Assistant Professor at UPS for two years (1981-1983). Since 1984, he has a permanent position at "Centre national de la recherche scientifique (CNRS)" and works at "Laboratoire des signaux et systèmes (L2S)" at Centrale-Supélec. He was a visiting Associate Professor at University of Notre Dame, Indiana, USA during 1997-1998. From 1998 to 2002, he has been at the head of Signal and Image Processing division at this laboratory.
Abstract:
There have been recent advances in different techniques of Mass spectrometry. However, in many of these techniques there are common mathematical framework: Inverse problems. In this work, a few of these inverse problems are presented and an overview of the methods to handle them is given. The Bayesian inference approach is a very useful approach to handle these problems as it give the possibility to account both for prior modeling of the signals and images and for the uncertainly associated to the measurement process. It also gives the necessary tools to estimate the hyper parameters and the remaining uncertainties in the proposed solution. To illustrate this, we take the deconvolution problem which is one of the main inverse problems in mass spectrometry and go through the different regularization and Bayesian inference methods and compare their relative performances.
Keynote Forum
Achille Cappiello
LC-MS Laboratory, University of Urbino, Italy
Keynote: Liquid-EI interface: a new concept to enhance performance and stability in liquid chromatography-electron ionization mass spectrometry
Time : 9:30- 10:00
Biography:
Achille Cappiello is a professor of Analytical Chemistry at the University of Urbino in Italy, He studied at the University of Rome La Sapienza and after a two-year appointment as Post Doctoral Associate at the Massachusetts Institute of Technology, supervised by Professor Klaus Biemann, he began to engage in the field of LC-MS. Professor Cappiello is the director of several projects dealing with LC-MS instrument development and design with some of the major manufacturers. He published more than 100 scientific articles with an international circulation including the top journals in the field such as “Analytical Chemistry” and “Mass Spectrometry Reviews”.
Abstract:
A novel liquid chromatography-mass spectrometry (LC-MS) interfacing concept is presented and discussed. The new interface design is called “Liquid-EI”, LEI to distinguish it from previous attempts. In a LEI interface, vaporization of the HPLC eluate is carried out inside a suitable, independent micro-channel right before entering the ion source. An inert gas flow carries the gas phase molecules into the ion source. This approach moves the solute vaporization event immediately outside the ion source into a more suitable space in terms of dimensions, temperatures and surface materials, and free of sensitive components and electric potentials. The pressure drop and temperature gradients between LC and MS can be carefully monitored and controlled to enhance analyte response and reduce band broadening and/or solute carryovers. Preliminary results, carried out using an Agilent 7010 QqQ mass spectrometer and 5975 single quadrupole, gave us an optimistic impression, especially when the vaporization micro-channel was covered with a ceramic layer. Proof of concept and detailed description of the interface are presented. Preliminary experiments were conducted using PAHs (2-6 rings) and other compounds of environmental interest with and without column separation. Real world samples were analyzed using LEI with particular emphasis to address issues on identification of metabolites at low levels where mass spectral quality using high resolution accurate mass (HRAM) can be an issue and NMR may prove challenging, and further, complex sample matrix (soil, vegetable, food and other bio matrices, etc..) can give additional difficulties.
Keynote Forum
Wenjie Cao
SABIC Technology Center, Saudi Arabia
Keynote: From ESI to APCI, MMI and APPI, Complications of Adduct Ions on MRM at Different LC-MS/MS Ionization Techniques
Time : 9:00- 9:30
Biography:
Wenjie Cao received Ph.D. from Professor John Calvin Giddings’ Group at the University of Utah, Salt Lake City, UT. Contributor to the book of the Encyclopedia of Chromatography and more than 20 publications and presentations in peer-reviewed scientific journals and international conferences. Had worked for Huntsman Polymers Corp, Sealed Air Corp, and DuPont, as a Research Investigator, for 14 years in USA before joined SABIC in 2012. Now the Technical Leader of the Chromatography and Wet Lab and a Staff Scientist of the Analytical Department of the SABIC Technology Center at Riyadh, have filed six patents and delivered talks and made seminar presentations in the ISPAC Symposium 2016 and in King Saud University etc. since joint SABIC Technology Center.
Abstract:
This presentation is going to extend the comparison of ESI and APCI to MMI and APPI per some of the audiences’ request during the Q&A section of my presentation during the 2015 International Summit on Current Trend of MS in New Orleans. For the triple quadrupole LC-MS/MS instrument, the primary purpose or the most significant feature is the highest sensitivity among almost all, if not all, of the LC-MS/MS instruments by doing the Multiple Reaction Monitoring (MRM) testing. Ionization efficiency, selectivity, adduct ion production are among the top parameters which affect the MRM testing and the sensitivity. From ESI to APCI to MMI and APPI, this presentation will show the species and amount of adduct ions produced at each mode are quite different. Some type of the adduct ions may complicate the MRM testing by decreasing the sensitivities while some other adduct ions may prevent any reliable MRM tests being performed. Some examples will be presented to show how the typical adduct ions are produced in each mode from ESI to APCI and APPI, and how the typical adduct ions may complicate the MRM testing. The overall pros and cons, and the best ionization mode for some type of the targeted chemicals will be summarized for the different ionization techniques.
Keynote Forum
K.W. Michael Siu
University of Windsor, Canada
Keynote: Gas-Phase Dehydration of Protonated Polyglycines
Time : 9:30- 10:00
Biography:
Dr. Siu then accepted a position as Research Associate with the Division of Chemistry at the National Research Council of Canada. Over the following 16 years, Dr. Siu held positions with the NRC as Research Officer, Institute for Environmental Research and Technology (formerly Institute for Environmental Chemistry) and Senior Research Officer, Institute for National Measurement Standards. In 1998, Dr. Siu relocated to York University as Professor of Chemistry and NSERC/SCIEX (now AB SCIEX) Senior Industrial Research Chair in Analytical Mass Spectrometry. He was the Founding Director of the Centre for Research in Mass Spectrometry. Dr. Siu was named Distinguished Research Professor in 2007; in July of 2005, he accepted the first of two, three-year appointments as the Associate Vice-President Research, Science and Technology at York University. Dr. Siu is recognized globally as a leader in the fundamentals as well as applications in the field of mass spectrometry. He has coauthored more than 240 refereed articles, and he and his group have given in excess of 440 presentations of which 50% were in the invited, keynote or plenary category.
Abstract:
Loss of water is a common reaction after collisional activation of protonated polypeptides. We selected polyglycines as prototypical polypeptides for examination of the source of the water loss. Polyglycines labeled with 18O at specific peptide linkages were custom-synthesized using Wang resin. Protonated tetraglycine loses water predominantly from its first peptide linkage. Loss of water from the second peptide linkage increases in abundance with increasing peptide length, and becomes the predominant channel in hexaglycine. For tetraglycine, both density functional theory (DFT) calculations and infrared multiple photon dissociation (IRMPD) experiment strongly suggest that the dehydration product is formed by loss of water from the first peptide bond that results in a protonated imidazole-4-one (U.H. Verkerk et al. J. Phys. Chem. A 2011, 115, 6683; J.K.-C. Lau et al. Int. J. Mass Spectrom. 2012, 316, 268). Preliminary DFT and collision-induced dissociation (CID) results continue to support this structural interpretation for the dehydration products of pentaglycine and hexaglycine that involve loss of water from the first peptide bond. Those results that involve water loss from the second peptide bond suggest a series of rearrangement reactions prior to dissociation. Our results thus far indicate multiple pathways of polyglycine dehydration that are competitive.