Day 1 :
- New Approaches in Mass Spectrometry|Recent Advances and Developments|Ionization Techniques|Mass Spectrometry in Proteomic Research
Session Introduction
Makhapa Makhafola
Research & Development, Mintek, South Africa
Title: The assessment of the exposure levels to mycotoxins in dairy cattle in the two South African provinces using HPLC (ESI)-MS/MSn
Biography:
Makhapa Makhafola is currently the General Manager of Research & Development at Mintek.
Abstract:
Mycotoxins can be formed on crops in the field, during harvest or during storage, processing or feeding. Many different mycotoxins exist and they affect dairy cattle in many ways, the most important is perhaps immunosuppression. Symptoms of mycotoxins may be non-specific and wide ranging which may include: Reduced production, reduced feed consumption, intermittent diarrhea (sometimes with bloody or dark manure), reduced feed intake, thriftiness, rough hair coat, reduced reproductive performance including irregular oestrus cycles and embryonic mortalities. While mycotoxins can cause acute toxicity, they are more likely to cause chronic problems of increased disease and decreased milk production. Contamination of milk by aflatoxin can cause huge economic losses. Management of crops and feeds is important to reduce mycotoxin contamination. The levels and nature of mycotoxins and some of their main metabolites in dairy feed, raw milk and urine samples collected from some dairy cattle farms are currently being assessed and will be discussed in detail. The research project aims to generate data to propose recommendation to the South African government on the threat of mycotoxins contamination to animal and human health.
G Simões
Instituto de QuÃmica, Rio de Janeiro, Brazil.
Title: The use of mass spectrometry and spectroscopic techniques to study sulfur consisting biomolecules
Biography:
Clemens Schwarzinger Johannes Kepler University Linz, Austria
Abstract:
In recent years, there has been a large interest in the study of biological systems, namely, amino acids, peptides, and proteins, using synchrotron-based spectroscopic techniques, such as near-edge X-ray absorption fine structure (NEXAFS) or related X-ray photoelectron and X-ray emission spectroscopies. Most of the X-ray spectroscopic investigations of biologically relevant molecules, such as amino acids and their polymers, have been performed on thin organic films and liquids [1].The association of mass spectrometry and spectroscopic techniques has allowed for the investigation of the effects of radiation damage insulfur containing molecules. We have performed a NEXAFS (S1s) and mass spectrometry study of solid samples of cysteine, cystine and insulin irradiated with 0.8 keV electrons. The measured mass spectra point out to processes of desulfurization, deamination, decarbonylation and decarboxylation in the irradiated biomolecules [2].In another study, inner-shell measurements of insulin were performed by coupling a linear ion trap mass spectrometer, equipped with an ESI source at the french synchrotron radiation facility SOLEIL. Theelectrosprayed insulin ions were injected, mass selected, stored in the trap, and irradiated during a well-defined period.The near-edge X-ray ion yield spectra of the 6+ charge state insulin precursorwere recorded as a function of the photon energy, in the vicinity of the C1s edge.
Alex Parmar
Masters of Engineer In Embedded Systems Institute of Technology, Nirma University On Behalf of Atonarp Microsystem Pvt. Ltd.
Title: Automated Production Validation Using Analytics
Biography:
Alex Parmar is a Student in Masters of Engineer In Embedded Systems at Institute of Technology, Nirma University On Behalf of Atonarp Microsystem Pvt. Ltd.
Abstract:
The Mass Spectrometer is widely use in Pharmaceutical and Semiconductor Fabrication facility. The main goal of Mass Spectrometer is to measure the amount of elements present in the gas chamber.Gas Chamber is the input of the device where blend of gas, Atmospheric Air, Fab-lab vacuum chamber and Pharmaceutical production line.
ATONARP Mass Spectrometer have different kind of electronics components, and the working of each component defines the accuracy of Spectrum. That components are used in different kind of Electronics PCB boards, each board has a specific purpose. In AMS There are main 2 parts which is Controller Box and Power Entry Boards.
Power Entry Boards consist Power entry Base board and Daughter boards 1 and 2, where Controller box consist RF Drive Board, Ion Drive Board, Ion Detector, Power Supply Board, Front panel Board and Baseboard
Functionality of each board is checked by test case.A test case is developed based on the functionality which user wants in the device. For different Boards there will be multiple Features. Test case run on each available system as well as on Emulator and the data of the test-case is stores in Master.log file. A script is developed to abstract that data from Master.log file to .csv file and based on that result the Key performance index is defined.
Magnus S Magnusson
University of Iceland, Iceland
Title: Similarity of hierarchical structured clustering in human and neuronal interactions & on DNA: Structural and functional analogies
Biography:
Magnus S Magnusson is a Research Professor have received his PhD in 1983 from University of Copenhagen. Author of the T-pattern model and the corresponding detection algorithms in THEME. He has focused on real-time organization of behavior, co-directed DNA analysis, numerous papers and invited talks at numerous conferences and universities in Europe, USA and Japan. Deputy Director 1983-1988, Anthropology Laboratory, Museum of Natural History, Paris.Repeatedly invited temporary Professor at the University of Paris.Since 1991, Founder and Director of the Human Behavior Laboratory, University of Iceland. Since 1995, he is in collaboration between 24 universities based on “Magnusson’s analytical model” initiated at the Sorbonne, Paris.
Abstract:
Hierarchical structured clustering (HSC) seems characteristic of the structure of the universebalancing a small number of forces, some pulling others pushing apart, the self-similar fractal distribution of matter in the universe thus reflecting HST rather than just dispersion or clumping. HSC also characterizes a proposed pattern type, called T-pattern, detected in the temporal organization of many kinds of verbal and non-verbal human, animal and neuronal behavior and interactions and is also characteristic of the structure of DNA. Functional analogies seem to exist between the occurrence of T-patterns in “cell city” and in human cities. Structural self-similarity over many levels of biological organization suggests the possibility of a unified (mathematical, bioinformatics and system biological) approach. The T-patternis described as a repeated hierarchical and self-similar tree structure based on a single non-terminal relation, called a critical interval (CI) relationship. Theinstancesof a T-pattern may be seen as repeated statistical pseudo-fractal objects characterized by statistically significant translation symmetry. THEMEtm (by M.S. Magnusson, ©PatternVision Ltd) is special purpose T-pattern detection and analysis PC software using a specialCI detection algorithm combined with an evolution algorithm, presented here together with results from the analysis of behaviorand interactions.From the relatively slow time scale of human and animal interactions to the much faster interactions within populations of neurons in living rat brains. Analogies are discussed between T-pattern structure and functions in the cities of proteins (cell city) and human cities, especially regarding specialization and the particular case of religious behavior.
Biography:
Brigitte Simons is a market development specialist at SCIEX, specializing in metabolomics using accurate mass time-of-flight mass spectrometry solutions. Prior to working at SCIEX, Brigitte received her Ph.D. in Chemical Biology at the University of Ottawa. She then completed two research post-doctoral fellowships at the Centre for Biologics Research at Health Canada and the National Institute of Heart Lung and Blood in Bethesda MD. Brigitte also spearheads an academic partnerships program for our North American business – which listeners can browse sciex.com for more information or contact Brigitte for more information.
Abstract:
This presentation will address technologies that directly address clinical research experimentation of lipids in tissue extracts, keeping sampling and data processing throughput in mind. The human lipidome contains >100,000 different molecular species found within a small mass range; consequently, isobaric overlap makes unambiguous identification and quantitation of lipid species difficult. Herein, methods that utilize high sensitivity MS/MS techniques using a high sensitivity triple quadrupole linked LIT mass spectrometer to isolate lipid classes for identification of molecular composition and quantitation have been investigated. Furthermore, QqQ platforms can now be coupled to differential ion mobility (DMS) devices and have shown to resolve phospholipid sub-classes, triglycerides, and strikingly, the sphingomyelins (SM) were resolved from PC molecular species. The latter observation is significant considering these two classes cannot be resolved using triple quadrupole strategies alone, and their masses overlap significantly. Alterations in hepatic phospholipid composition, especially the amount of phosphatidylcholine (PC) and the ratio of PC to phosphatidylanolamine (PE) might contribute to the development nonalcoholic fatty liver disease (NAFLD). Aim was to compare PC/PE ratio in patients with NAFLD or chronic Hepatitis C (CHC) to healthy controls. This was a cross-sectional study. Liver samples were obtained from healthy controls (HC), patients with simple steatosis (SS), and steatohepatitis (NASH). Lipids were extracted from liver tissue and the total PC and PE lipid detected was quantified by tandem mass spectrometry using multiple precursor ion scanning [normalized by internal standards]. Hepatic PC/PE ratio was lower in all 3 patient groups, mainly due to a reduction in PC, which was significant in SS and NASH compared to controls. This study confirms previous animal data on PC/PE in NAFLD and represents a high throughput lipidomics platform’s utility to clinical outputs.
Elliot R Bernstein
Colorado State University, USA
Title: EUV laser mass spectrometry and photoelectron spectroscopy of mass selected neutral clusters & molecules
Biography:
Bernstein received his Ph.D. degree from Caltech and was a post doctoral fellow at the University of Chicago. He has been at CSU since 1975 where he has studied molecular crystal vibrational and electronic excitons and phase transitions, cryogenic liquids, and gas phase clusters with a central focus on intermolecular interactions. Recently his research has focused on chemical reactions of neutral and ionic clusters. This latter research area has involved catalytic and photocatalytic cluster systems, solute/solvent systems, the reactions of ionized molecules and clusters, and initial steps in the release of stored energy molecular species.
Abstract:
A long standing set of goals for studies of systems of inhomogeneous, neutral clusters (e.g., MmXn or (molecule)p) has been to mass sort and select them individually for determination of physical and chemical properties of each neutral cluster by spectroscopic techniques. We have constructed appropriate instrumentation to achieve these important goals employing photoelectron spectroscopy (PES), driven by both visible (for MmXn-) and EUV (for MmXn0) radiation. Our 26.5 eV/photon EUV laser can ionize any neutral cluster or molecule (EUV PES) that can be identified and isolated. The algorithm includes the following steps: 1. generation of cluster negative ions in a laser ablation supersonic source with the addition, as required, of low energy electrons from a Y2O3 disk; 2. separation of these anionic clusters in a reflectron time of flight mass spectrometer (RTOFMS); 3.selection and slowing of specific, chosen clusters in a mass gate/momentum deceleration stage; 4.threshold photo-detachment of the sorted and selected negative ion clusters with a tunable VIS/UV laser to generate neutral, isolated clusters; and 5. EUV PES of these neutral clusters. Such studies generate vibrational and structural information on the ground states of the neutral clusters (through VIS/UV PES), and information on the ion states of the clusters (through EUV PES). The presentation will include PES results on various metal oxides, sulfides, and other cluster systems and molecules.
Eduard Rogatsky
Wadsworth Center, USA
Title: Quantitative analysis of 25 Hydroxy vitamin D by LC/MS-assay standardization surprises
Biography:
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:
Vitamin D deficiency is a widespread clinical problem and has been associated with many adverse health outcomes. Analysis of Vitamin D2 (ergocalciferol) and D3 (cholecalciferol) and their major metabolites 25(OH)D2 and 25(OH)D3 has become a high priority topic in clinical analysis. Currently a variety of LC/MS methods have been developed to support vitamin D analysis. These LC/MS methods utilize different transitions, ionization modes, sample preparation strategies, mobile phases and columns. In LC/MS analysis of 25 OH Vitamin D, dehydration (water loss) is the major side reaction. Comparing acetonitrile to methanol, which are typically used as mobile phases for LC separation, acetonitrile does not support hydrogen bond formation; therefore, proton-induced water elimination in-source becomes a major side-reaction, especially given the low pH of the mobile phase and positive mode electrospray and APCI ionization. MeOH, in contrast, supports hydrogen bond formation with the 25(OH)D2 and 25(OH)D3 hydroxyl groups. This efficiently “shields” most of hydroxyl groups by hydrogen bonding, and protects against protonation and resultant water elimination. We found that quantitation of the 25(OH)D from its [M+H]+, “intact” precursor ion, is temperature invariant. In contrast, quantitation using the in-source dehydrated precursor (parent) ion, leads to increased sensitivity with a rise in temperature, due to its better ionization efficiency at higher temperatures. Since droplets evaporation region can vary with mass spectrometer hardware design, ratio between intact [M+H]+ and dehydrated precursor can be unpredictable. We also noticed that degree of dehydration is concentrationdependent. Chromatographic separation between analyte and its deuterated internal standard might cause different levels of analyte and internal standard dehydration and resulted in quantitative error.
S K Patel
Shree S. K. Patel College of Pharmaceutical Education and Research, Ganpat University, Gujarat, India
Title: Development and validation of bioanalytical method for estimation of methoxsalen present in human plasma
Biography:
S K Patel has completed her PhD from Ganpat University, Gujarat, India. She is an Assistant Professor in Quality Assurance Department, Shree S. K. Patel College of Pharmaceutical Education and Research, Ganpat University, Gujarat, India since last 10 years. She has published more than 37 papers in reputed national and international journals.
Abstract:
In this study, an attempt was made to describe and validate a liquid chromatography coupled with tandem mass spectrometry method for the quantification of methoxsalen, an antipsoriatic agent in human EDTA K3 plasma according to the current bioanalytical guidelines. The internal standard used was methoxsalen D3. The separation was performed on a Symmetry, C18, 4.6X 150 mm, 5 μm column using a mobile phase of 2 mM ammonium acetate and methanol 15:85 (v/v) with a flow rate of 0.80 ml/min. The detection of methoxsalen and the internal standard was performed in multiple reactions monitoring (MRM) mode using LC/MS/MS Mass Spectrometer with electro spray ionization, operating in positive ion mode. The human plasma samples were extracted using liquid-liquid extraction with methyl tert-butyl ether. The method shows a good linearity (R2 > 0.98), precision and accuracy over the range of 0.1-100 ng/ml methoxsalen in plasma. The recovery was between 93.85 and 105.25%. The limit of quantification was 0.1 ng/ml. The analysis required about 3.2 minutes run with retention time of drug 2.2 minutes. The proposed method was selective, sensitive, accurate and precise enough to be successfully applied to bioequivalence study.
Peter Mikuš
Comenius University in Bratislava, Slovakia
Title: Hyphenated two-dimensional chiral capillary electrophoresis - Tandem mass spectrometry method for ultra-trace determination of antihistamine enantiomers in biological samples
Biography:
Peter Mikuš has completed his PhD from Comenius University (Slovakia). He is researcher, University teacher, Associated Professor, and Director of the Toxicological and Antidoping Center at the Faculty of Pharmacy Comenius University in Bratislava (FPCU) as well as head of the Department of Pharmaceutical Analysis and Nuclear Pharmacy FPCU. A research team of P.M. is focused on the development, validation and application of advanced hyphenated analytical methods, based on a combination of 2D-separation and spectral (UV-VIS, MS/MS) techniques, for pharmaceutical and biomedical research. He has published more than 60 papers in reputed CC journals.
Abstract:
A chemical vapor generation (CVG) method is developed for determination of cadmium (Cd) by ICP-MS. Titanium (III) and titanium (IV) were utilized for the first time as novel additives to enhance generation of volatile Cd species, and their synergistic effects were investigated for thiourea, L-cysteine and potassium cyanide (KCN) with different mineral acids. Both Ti (III) and Ti (IV) provided the highest enhancement with KCN. The improvement with thiourea was marginal (ca. 2-fold), while L-cysteine boosted signals slightly only with Ti (III) in H2 SO4 . Optimum CVG conditions were 4% HCl + 0.03 M Ti(III) + 0.16 M KCN and 2% HNO3 + 0.03 M Ti(IV) + 0.16 M KCN. A 3% (m/v) NaBH4 solution was adequate for successful vapor generation. Under these conditions, sensitivity was enhanced 40-fold with Ti(III) and 35-fold with Ti(IV), that are the highest enhancement factors achieved so far in Cd vapor generation. Detection limits (3s) were 3.2 and 6.4 ng L-1 for 111Cd isotope using Ti(III) and Ti(IV), respectively. Evidence indicated that Ti (III) and Ti(IV) enhanced Cd vapor generation catalytically. Effects of transition metal ions, including Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II) and Zn(II) were not significant up to 1.0 µg mL-1. Among hydride forming elements, Bi, Pb, Sb and Sn depressed signals above 0.1 µg mL-1. No interferences were observed from As(III) and Se(IV). The method was validated with determination of Cd by CVG-ICP-MS in certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), Dogfish liver (DOLT-4), Mussel tissue (SRM 2976) and Domestic Sludge (SRM 2781).
Biography:
Zikri Arslan received his PhD in 2000 from the University of Massachusetts at Amherst in analytical chemistry with an emphasis on applied plasma source mass spectrometry. He was a National Research Council (NRC) post-doctoral scholar between 2000 and 2002; worked at NOAA/NEFSC Howard Marine Sciences Laboratory in Sandy Hook, NJ. He also worked as research scientist (2002-2003) at the University of Maryland, Chesapeake Biological Laboratory on otolith micromilling protocols for identification of bluefin tuna stocks. His research interests span from nanoparticle detection to analytical method development involving plasma spectrometry. He published more than 50 papers, served as guest editor and reviewer for major analytical and environmental chemistry journals.
Abstract:
A chemical vapor generation (CVG) method is developed for determination of cadmium (Cd) by ICP-MS. Titanium (III) and titanium (IV) were utilized for the first time as novel additives to enhance generation of volatile Cd species, and their synergistic effects were investigated for thiourea, L-cysteine and potassium cyanide (KCN) with different mineral acids. Both Ti (III) and Ti (IV) provided the highest enhancement with KCN. The improvement with thiourea was marginal (ca. 2-fold), while L-cysteine boosted signals slightly only with Ti (III) in H2 SO4 . Optimum CVG conditions were 4% HCl + 0.03 M Ti(III) + 0.16 M KCN and 2% HNO3 + 0.03 M Ti(IV) + 0.16 M KCN. A 3% (m/v) NaBH4 solution was adequate for successful vapor generation. Under these conditions, sensitivity was enhanced 40-fold with Ti(III) and 35-fold with Ti(IV), that are the highest enhancement factors achieved so far in Cd vapor generation. Detection limits (3s) were 3.2 and 6.4 ng L-1 for 111Cd isotope using Ti(III) and Ti(IV), respectively. Evidence indicated that Ti (III) and Ti(IV) enhanced Cd vapor generation catalytically. Effects of transition metal ions, including Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II) and Zn(II) were not significant up to 1.0 µg mL-1. Among hydride forming elements, Bi, Pb, Sb and Sn depressed signals above 0.1 µg mL-1. No interferences were observed from As(III) and Se(IV). The method was validated with determination of Cd by CVG-ICP-MS in certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), Dogfish liver (DOLT-4), Mussel tissue (SRM 2976) and Domestic Sludge (SRM 2781).