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Sample records for mass spectrometry effect

  1. Damping effects in Penning trap mass spectrometry

    CERN Document Server

    George, S; Kowalska, M; Dworschak, M; Neidherr, D; Blaum, K; Schweikhard, L; Ramirez, E M; Breitenfeldt, M; Kretzschmar, M; Herfurth, F; Schwarz, S; Herlert, A

    2011-01-01

    Collisions of ions with residual gas atoms in a Penning trap can have a strong influence on the trajectories of the ions, depending on the atom species and the gas pressure. We report on investigations of damping effects in time-of-flight ion-cyclotron resonance mass spectrometry with the Penning trap mass spectrometers ISOLTRAP at ISOLDE/CERN (Geneva, Switzerland) and SHIPTRAP at GSI (Darmstadt, Germany). The work focuses on the interconversion of the magnetron and cyclotron motional modes, in particular the modification of the resonance profiles for quadrupolar excitation due to the damping effect of the residual gas. Extensive experiments have been performed with standard and Ramsey excitation schemes. The results are in good agreement with predictions obtained by analytical continuation of the formulae for the undamped case.

  2. Mass spectrometry

    DEFF Research Database (Denmark)

    Nyvang Hartmeyer, Gitte; Jensen, Anne Kvistholm; Böcher, Sidsel

    2010-01-01

    Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) is currently being introduced for the rapid and accurate identification of bacteria. We describe 2 MALDI-TOF MS identification cases - 1 directly on spinal fluid and 1 on grown bacteria. Rapidly obtained r...

  3. Understanding ligand effects in gold clusters using mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Grant E.; Laskin, Julia

    2016-01-01

    This review summarizes recent research on the influence of phosphine ligands on the size, stability, and reactivity of gold clusters synthesized in solution. Sub-nanometer clusters exhibit size- and composition-dependent properties that are unique from those of larger nanoparticles. The highly tunable properties of clusters and their high surface-to-volume ratio make them promising candidates for a variety of technological applications. However, because “each-atom-counts” toward defining cluster properties it is critically important to develop robust synthesis methods to efficiently prepare clusters of predetermined size. For decades phosphines have been known to direct the size-selected synthesis of gold clusters. Despite the preparation of numerous species it is still not understood how different functional groups at phosphine centers affect the size and properties of gold clusters. Using electrospray ionization mass spectrometry (ESI-MS) it is possible to characterize the effect of ligand substitution on the distribution of clusters formed in solution at defined reaction conditions. In addition, ligand exchange reactions on preformed clusters may be monitored using ESI-MS. Collision induced dissociation (CID) may also be employed to obtain qualitative insight into the fragmentation of mixed ligand clusters and the relative binding energies of differently substituted phosphines. Quantitative ligand binding energies and cluster stability may be determined employing surface induced dissociation (SID) in a custom-built Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS). Rice-Ramsperger-Kassel-Marcus (RRKM) based modeling of the SID data allows dissociation energies and entropy values to be extracted that may be compared with the results of high-level theoretical calculations. The charge reduction and reactivity of atomically precise gold clusters, including partially ligated species generated in the gas-phase by in source CID, on well

  4. Understanding ligand effects in gold clusters using mass spectrometry.

    Science.gov (United States)

    Johnson, Grant E; Laskin, Julia

    2016-06-21

    This review summarizes recent research on the influence of phosphine ligands on the size, stability, and reactivity of gold clusters synthesized in solution. Sub-nanometer clusters exhibit size- and composition-dependent properties that are unique from those of larger nanoparticles. The highly tunable properties of clusters and their high surface-to-volume ratio make them promising candidates for a variety of technological applications. However, because "each-atom-counts" toward defining cluster properties it is critically important to develop robust synthesis methods to efficiently prepare clusters of predetermined size. For decades phosphines have been known to direct the size-selected synthesis of gold clusters. Despite the preparation of numerous species it is still not understood how different functional groups at phosphine centers affect the size and properties of gold clusters. Using electrospray ionization mass spectrometry (ESI-MS) it is possible to characterize the effect of ligand substitution on the distribution of clusters formed in solution at defined reaction conditions. In addition, ligand exchange reactions on preformed clusters may be monitored using ESI-MS. Collision induced dissociation (CID) may also be employed to obtain qualitative insight into the fragmentation of mixed ligand clusters and the relative binding energies of differently substituted phosphines. Quantitative ligand binding energies and cluster stability may be determined employing surface induced dissociation (SID) in a custom-built Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS). Rice-Ramsperger-Kassel-Marcus (RRKM) based modeling of the SID data allows dissociation energies and entropy values to be extracted. The charge reduction and reactivity of atomically precise gold clusters, including partially ligated species generated in the gas-phase by in source CID, on well-defined surfaces may be explored using ion soft landing (SL) in a custom

  5. Fourier transform mass spectrometry.

    Science.gov (United States)

    Scigelova, Michaela; Hornshaw, Martin; Giannakopulos, Anastassios; Makarov, Alexander

    2011-07-01

    This article provides an introduction to Fourier transform-based mass spectrometry. The key performance characteristics of Fourier transform-based mass spectrometry, mass accuracy and resolution, are presented in the view of how they impact the interpretation of measurements in proteomic applications. The theory and principles of operation of two types of mass analyzer, Fourier transform ion cyclotron resonance and Orbitrap, are described. Major benefits as well as limitations of Fourier transform-based mass spectrometry technology are discussed in the context of practical sample analysis, and illustrated with examples included as figures in this text and in the accompanying slide set. Comparisons highlighting the performance differences between the two mass analyzers are made where deemed useful in assisting the user with choosing the most appropriate technology for an application. Recent developments of these high-performing mass spectrometers are mentioned to provide a future outlook.

  6. Forensic Mass Spectrometry

    Science.gov (United States)

    Hoffmann, William D.; Jackson, Glen P.

    2015-07-01

    Developments in forensic mass spectrometry tend to follow, rather than lead, the developments in other disciplines. Examples of techniques having forensic potential born independently of forensic applications include ambient ionization, imaging mass spectrometry, isotope ratio mass spectrometry, portable mass spectrometers, and hyphenated chromatography-mass spectrometry instruments, to name a few. Forensic science has the potential to benefit enormously from developments that are funded by other means, if only the infrastructure and personnel existed to adopt, validate, and implement the new technologies into casework. Perhaps one unique area in which forensic science is at the cutting edge is in the area of chemometrics and the determination of likelihood ratios for the evaluation of the weight of evidence. Such statistical techniques have been developed most extensively for ignitable-liquid residue analyses and isotope ratio analysis. This review attempts to capture the trends, motivating forces, and likely impact of developing areas of forensic mass spectrometry, with the caveat that none of this research is likely to have any real impact in the forensic community unless: (a) The instruments developed are turned into robust black boxes with red and green lights for positives and negatives, respectively, or (b) there are PhD graduates in the workforce who can help adopt these sophisticated techniques.

  7. Miniaturization and Mass Spectrometry

    NARCIS (Netherlands)

    le Gac, S.; le Gac, Severine; van den Berg, Albert; van den Berg, A.; Unknown, [Unknown

    2009-01-01

    With this book we want to illustrate how two quickly growing fields of instrumentation and technology, both applied to life sciences, mass spectrometry and microfluidics (or microfabrication) naturally came to meet at the end of the last century and how this marriage impacts on several types of appl

  8. Analytical mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    This 43rd Annual Summer Symposium on Analytical Chemistry was held July 24--27, 1990 at Oak Ridge, TN and contained sessions on the following topics: Fundamentals of Analytical Mass Spectrometry (MS), MS in the National Laboratories, Lasers and Fourier Transform Methods, Future of MS, New Ionization and LC/MS Methods, and an extra session. (WET)

  9. Analytical mass spectrometry. Abstracts

    Energy Technology Data Exchange (ETDEWEB)

    1990-12-31

    This 43rd Annual Summer Symposium on Analytical Chemistry was held July 24--27, 1990 at Oak Ridge, TN and contained sessions on the following topics: Fundamentals of Analytical Mass Spectrometry (MS), MS in the National Laboratories, Lasers and Fourier Transform Methods, Future of MS, New Ionization and LC/MS Methods, and an extra session. (WET)

  10. Matrix effects in inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xiaoshan [Iowa State Univ., Ames, IA (United States)

    1995-07-07

    The inductively coupled plasma is an electrodeless discharge in a gas (usually Ar) at atmospheric pressure. Radio frequency energy generated by a RF power source is inductively coupled to the plasma gas through a water cooled load coil. In ICP-MS the "Fassel" TAX quartz torch commonly used in emission is mounted horizontally. The sample aerosol is introduced into the central flow, where the gas kinetic temperature is about 5000 K. The aerosol is vaporized, atomized, excited and ionized in the plasma, and the ions are subsequently extracted through two metal apertures (sampler and skimmer) into the mass spectrometer. In ICP-MS, the matrix effects, or non-spectroscopic interferences, can be defined as the type of interferences caused by dissolved concomitant salt ions in the solution. Matrix effects can be divided into two categories: (1) signal drift due to the deposition of solids on the sampling apertures; and/or (2) signal suppression or enhancement by the presence of the dissolved salts. The first category is now reasonably understood. The dissolved salts, especially refractory oxides, tend to deposit on the cool tip of the sampling cone. The clogging of the orifices reduces the ion flow into the ICP-MS, lowers the pressure in the first stage of ICP-MS, and enhances the level of metal oxide ions. Because the extent of the clogging increases with the time, the signal drifts down. Even at the very early stage of the development of ICP-MS, matrix effects had been observed. Houk et al. found out that the ICP-MS was not tolerant to solutions containing significant amounts of dissolved solids.

  11. Mass spectrometry with accelerators.

    Science.gov (United States)

    Litherland, A E; Zhao, X-L; Kieser, W E

    2011-01-01

    As one in a series of articles on Canadian contributions to mass spectrometry, this review begins with an outline of the history of accelerator mass spectrometry (AMS), noting roles played by researchers at three Canadian AMS laboratories. After a description of the unique features of AMS, three examples, (14)C, (10)Be, and (129)I are given to illustrate the methods. The capabilities of mass spectrometry have been extended by the addition of atomic isobar selection, molecular isobar attenuation, further ion acceleration, followed by ion detection and ion identification at essentially zero dark current or ion flux. This has been accomplished by exploiting the techniques and accelerators of atomic and nuclear physics. In 1939, the first principles of AMS were established using a cyclotron. In 1977 the selection of isobars in the ion source was established when it was shown that the (14)N(-) ion was very unstable, or extremely difficult to create, making a tandem electrostatic accelerator highly suitable for assisting the mass spectrometric measurement of the rare long-lived radioactive isotope (14)C in the environment. This observation, together with the large attenuation of the molecular isobars (13)CH(-) and (12)CH 2(-) during tandem acceleration and the observed very low background contamination from the ion source, was found to facilitate the mass spectrometry of (14)C to at least a level of (14)C/C ~ 6 × 10(-16), the equivalent of a radiocarbon age of 60,000 years. Tandem Accelerator Mass Spectrometry, or AMS, has now made possible the accurate radiocarbon dating of milligram-sized carbon samples by ion counting as well as dating and tracing with many other long-lived radioactive isotopes such as (10)Be, (26)Al, (36)Cl, and (129)I. The difficulty of obtaining large anion currents with low electron affinities and the difficulties of isobar separation, especially for the heavier mass ions, has prompted the use of molecular anions and the search for alternative

  12. Hydrogen Exchange Mass Spectrometry.

    Science.gov (United States)

    Mayne, Leland

    2016-01-01

    Hydrogen exchange (HX) methods can reveal much about the structure, energetics, and dynamics of proteins. The addition of mass spectrometry (MS) to an earlier fragmentation-separation HX analysis now extends HX studies to larger proteins at high structural resolution and can provide information not available before. This chapter discusses experimental aspects of HX labeling, especially with respect to the use of MS and the analysis of MS data.

  13. "Magic" Ionization Mass Spectrometry

    Science.gov (United States)

    Trimpin, Sarah

    2016-01-01

    The systematic study of the temperature and pressure dependence of matrix-assisted ionization (MAI) led us to the discovery of the seemingly impossible, initially explained by some reviewers as either sleight of hand or the misinterpretation by an overzealous young scientist of results reported many years before and having little utility. The "magic" that we were attempting to report was that with matrix assistance, molecules, at least as large as bovine serum albumin (66 kDa), are lifted into the gas phase as multiply charged ions simply by exposure of the matrix:analyte sample to the vacuum of a mass spectrometer. Applied heat, a laser, or voltages are not necessary to achieve charge states and ion abundances only previously observed with electrospray ionization (ESI). The fundamentals of how solid phase volatile or nonvolatile compounds are converted to gas-phase ions without added energy currently involves speculation providing a great opportunity to rethink mechanistic understanding of ionization processes used in mass spectrometry. Improved understanding of the mechanism(s) of these processes and their connection to ESI and matrix-assisted laser desorption/ionization may provide opportunities to further develop new ionization strategies for traditional and yet unforeseen applications of mass spectrometry. This Critical Insights article covers developments leading to the discovery of a seemingly magic ionization process that is simple to use, fast, sensitive, robust, and can be directly applied to surface characterization using portable or high performance mass spectrometers.

  14. Biomedical accelerator mass spectrometry

    Science.gov (United States)

    Freeman, Stewart P. H. T.; Vogel, John S.

    1995-05-01

    Ultrasensitive SIMS with accelerator based spectrometers has recently begun to be applied to biomedical problems. Certain very long-lived radioisotopes of very low natural abundances can be used to trace metabolism at environmental dose levels ( [greater-or-equal, slanted] z mol in mg samples). 14C in particular can be employed to label a myriad of compounds. Competing technologies typically require super environmental doses that can perturb the system under investigation, followed by uncertain extrapolation to the low dose regime. 41Ca and 26Al are also used as elemental tracers. Given the sensitivity of the accelerator method, care must be taken to avoid contamination of the mass spectrometer and the apparatus employed in prior sample handling including chemical separation. This infant field comprises the efforts of a dozen accelerator laboratories. The Center for Accelerator Mass Spectrometry has been particularly active. In addition to collaborating with groups further afield, we are researching the kinematics and binding of genotoxins in-house, and we support innovative uses of our capability in the disciplines of chemistry, pharmacology, nutrition and physiology within the University of California. The field can be expected to grow further given the numerous potential applications and the efforts of several groups and companies to integrate more the accelerator technology into biomedical research programs; the development of miniaturized accelerator systems and ion sources capable of interfacing to conventional HPLC and GMC, etc. apparatus for complementary chemical analysis is anticipated for biomedical laboratories.

  15. International Mass Spectrometry Society (IMSS).

    Science.gov (United States)

    Cooks, R G; Gelpi, E; Nibbering, N M

    2001-02-01

    This paper gives a brief description of the recently formalized International Mass Spectrometry Society (IMSS). It is presented here in order to increase awareness of the opportunities for collaboration in mass spectrometry in an international context. It also describes the recent 15th International Mass Spectrometry Conference, held August/September 2000, in Barcelona. Each of the authors is associated with the IMSS. The 15th Conference, which covers all of mass spectrometry on a triennial basis, was chaired by Professor Emilio Gelpi of the Instituto de Investigaciones Biomedicas, Barcelona. The outgoing and founding President of the IMSS is Professor Graham Cooks, Purdue University, and the incoming President is Professor Nico Nibbering, University of Amsterdam. Similar material has been provided to the Editors of other journals that cover mass spectrometry.

  16. Biological Matrix Effects in Quantitative Tandem Mass Spectrometry-Based Analytical Methods: Advancing Biomonitoring

    Science.gov (United States)

    Panuwet, Parinya; Hunter, Ronald E.; D’Souza, Priya E.; Chen, Xianyu; Radford, Samantha A.; Cohen, Jordan R.; Marder, M. Elizabeth; Kartavenka, Kostya; Ryan, P. Barry; Barr, Dana Boyd

    2015-01-01

    The ability to quantify levels of target analytes in biological samples accurately and precisely, in biomonitoring, involves the use of highly sensitive and selective instrumentation such as tandem mass spectrometers and a thorough understanding of highly variable matrix effects. Typically, matrix effects are caused by co-eluting matrix components that alter the ionization of target analytes as well as the chromatographic response of target analytes, leading to reduced or increased sensitivity of the analysis. Thus, before the desired accuracy and precision standards of laboratory data are achieved, these effects must be characterized and controlled. Here we present our review and observations of matrix effects encountered during the validation and implementation of tandem mass spectrometry-based analytical methods. We also provide systematic, comprehensive laboratory strategies needed to control challenges posed by matrix effects in order to ensure delivery of the most accurate data for biomonitoring studies assessing exposure to environmental toxicants. PMID:25562585

  17. Accelerator mass spectrometry.

    Science.gov (United States)

    Hellborg, Ragnar; Skog, Göran

    2008-01-01

    In this overview the technique of accelerator mass spectrometry (AMS) and its use are described. AMS is a highly sensitive method of counting atoms. It is used to detect very low concentrations of natural isotopic abundances (typically in the range between 10(-12) and 10(-16)) of both radionuclides and stable nuclides. The main advantages of AMS compared to conventional radiometric methods are the use of smaller samples (mg and even sub-mg size) and shorter measuring times (less than 1 hr). The equipment used for AMS is almost exclusively based on the electrostatic tandem accelerator, although some of the newest systems are based on a slightly different principle. Dedicated accelerators as well as older "nuclear physics machines" can be found in the 80 or so AMS laboratories in existence today. The most widely used isotope studied with AMS is 14C. Besides radiocarbon dating this isotope is used in climate studies, biomedicine applications and many other fields. More than 100,000 14C samples are measured per year. Other isotopes studied include 10Be, 26Al, 36Cl, 41Ca, 59Ni, 129I, U, and Pu. Although these measurements are important, the number of samples of these other isotopes measured each year is estimated to be less than 10% of the number of 14C samples.

  18. Sheath liquid effects in capillary high-performance liquid chromatography-electrospray mass spectrometry of oligonucleotides.

    Science.gov (United States)

    Huber, C G; Krajete, A

    2000-02-18

    Fused-silica capillary columns of 200 microm inner diameter were packed with micropellicular, octadecylated, 2.3 microm poly(styrene-divinylbenzene) particles and applied to the separation of oligonucleotides by ion-pair reversed-phase high-performance liquid chromatography. Oligonucleotides were eluted at 50 degrees C with gradients of 3-13% acetonitrile in 50 mM triethylammonium bicarbonate. Addition of sheath liquid to the column effluent allowed the detection of oligonucleotides by electrospray ionization mass spectrometry using full-scan data acquisition with a detectability comparable to that obtained with UV detection. The signal-to-noise ratios with different sheath liquids increased in the order isopropanoleffect was observed with shorter oligonucleotides. Organic acids and bases in the sheath liquid generally deteriorated the signal-to-noise ratios in the chromatograms and mass spectra mainly because of increased background noise. Only a few charge states were observed in the mass spectra of oligonucleotides because of charge state reduction due to the presence of carbonic acid in the eluent. With triethylammonium hydrogencarbonate as chromatographic eluent and acetonitrile as sheath liquid, very few cation adducts of oligonucleotides were observed in the mass spectra. However, the presence of small amounts of monopotassium adducts enabled the calculation of the charge state of multiply charged ions. With acetonitrile as sheath liquid, 710 amol of a 16-mer oligonucleotide were detected using selected ion monitoring data acquisition with a signal-to-noise ratio of 3:1. Finally, capillary ion-pair reversed-phase high-performance liquid chromatography-electrospray ionization mass spectrometry was

  19. Mass Spectrometry of Halopyrazolium Salts

    DEFF Research Database (Denmark)

    Larsen, Elfinn; Egsgaard, Helge; Pande, U. C.;

    1983-01-01

    Eleven halogen substituted 1-methyl-2-phenylpyrazolium bromides or chlorides were investigated by field desorption, field ionization, and electron impact mass spectrometry. Dealkylation was found to be the predominant thermal decomposition. An exchange between covalent and ionic halogen prior...

  20. Mass Spectrometry Applications for Toxicology

    Science.gov (United States)

    Mbughuni, Michael M.; Jannetto, Paul J.

    2016-01-01

    Toxicology is a multidisciplinary study of poisons, aimed to correlate the quantitative and qualitative relationships between poisons and their physiological and behavioural effects in living systems. Other key aspects of toxicology focus on elucidation of the mechanisms of action of poisons and development of remedies and treatment plans for associated toxic effects. In these endeavours, Mass spectrometry (MS) has become a powerful analytical technique with a wide range of application used in the Toxicological analysis of drugs, poisons, and metabolites of both. To date, MS applications have permeated all fields of toxicology which include; environmental, clinical, and forensic toxicology. While many different analytical applications are used in these fields, MS and its hyphenated applications such as; gas chromatography MS (GC-MS), liquid chromatography MS (LC-MS), inductively coupled plasma ionization MS (ICP-MS), tandem mass spectrometry (MS/MS and MSn) have emerged as powerful tools used in toxicology laboratories. This review will focus on these hyphenated MS technologies and their applications for toxicology.

  1. Mass Spectrometry Applications for Toxicology.

    Science.gov (United States)

    Mbughuni, Michael M; Jannetto, Paul J; Langman, Loralie J

    2016-12-01

    Toxicology is a multidisciplinary study of poisons, aimed to correlate the quantitative and qualitative relationships between poisons and their physiological and behavioural effects in living systems. Other key aspects of toxicology focus on elucidation of the mechanisms of action of poisons and development of remedies and treatment plans for associated toxic effects. In these endeavours, Mass spectrometry (MS) has become a powerful analytical technique with a wide range of application used in the Toxicological analysis of drugs, poisons, and metabolites of both. To date, MS applications have permeated all fields of toxicology which include; environmental, clinical, and forensic toxicology. While many different analytical applications are used in these fields, MS and its hyphenated applications such as; gas chromatography MS (GC-MS), liquid chromatography MS (LC-MS), inductively coupled plasma ionization MS (ICP-MS), tandem mass spectrometry (MS/MS and MS(n)) have emerged as powerful tools used in toxicology laboratories. This review will focus on these hyphenated MS technologies and their applications for toxicology.

  2. Mass spectrometry. [in organic chemistry

    Science.gov (United States)

    Burlingame, A. L.; Shackleton, C. H. L.; Howe, I.; Chizhov, O. S.

    1978-01-01

    A review of mass spectrometry in organic chemistry is given, dealing with advances in instrumentation and computer techniques, selected topics in gas-phase ion chemistry, and applications in such fields as biomedicine, natural-product studies, and environmental pollution analysis. Innovative techniques and instrumentation are discussed, along with chromatographic-mass spectrometric on-line computer techniques, mass spectral interpretation and management techniques, and such topics in gas-phase ion chemistry as electron-impact ionization and decomposition, photoionization, field ionization and desorption, high-pressure mass spectrometry, ion cyclotron resonance, and isomerization reactions of organic ions. Applications of mass spectrometry are examined with respect to bio-oligomers and their constituents, biomedically important substances, microbiology, environmental organic analysis, and organic geochemistry.

  3. Neuroscience and Accelerator Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Palmblad, M N; Buchholz, B A; Hillegonds, D J; Vogel, J S

    2004-08-02

    Accelerator mass spectrometry (AMS) is a mass spectrometric method for quantifying rare isotopes. It has had great impact in geochronology and archaeology and is now being applied in biomedicine. AMS measures radioisotopes such as {sup 3}H, {sup 14}C, {sup 26}Al, {sup 36}Cl and {sup 41}Ca, with zepto- or attomole sensitivity and high precision and throughput, enabling safe human pharmacokinetic studies involving: microgram doses, agents having low bioavailability, or toxicology studies where administered doses must be kept low (<1 {micro}g/kg). It is used to study long-term pharmacokinetics, to identify biomolecular interactions, to determine chronic and low-dose effects or molecular targets of neurotoxic substances, to quantify transport across the blood-brain barrier and to resolve molecular turnover rates in the human brain on the timescale of decades. We will here review how AMS is applied in neurotoxicology and neuroscience.

  4. Methods for recalibration of mass spectrometry data

    Science.gov (United States)

    Tolmachev, Aleksey V.; Smith, Richard D.

    2009-03-03

    Disclosed are methods for recalibrating mass spectrometry data that provide improvement in both mass accuracy and precision by adjusting for experimental variance in parameters that have a substantial impact on mass measurement accuracy. Optimal coefficients are determined using correlated pairs of mass values compiled by matching sets of measured and putative mass values that minimize overall effective mass error and mass error spread. Coefficients are subsequently used to correct mass values for peaks detected in the measured dataset, providing recalibration thereof. Sub-ppm mass measurement accuracy has been demonstrated on a complex fungal proteome after recalibration, providing improved confidence for peptide identifications.

  5. Glycolysis and respiration in yeasts. The Pasteur effect studied by mass spectrometry.

    Science.gov (United States)

    Lloyd, D; Kristensen, B; Degn, H

    1983-06-15

    Simultaneous and continuous measurements of changes in CO2 and O2 concentrations in glucose-metabolizing yeast suspensions by mass spectrometry enabled a study of the Pasteur effect (aerobic inhibition of glycolysis) in Saccharomyces uvarum and Schizosaccharomyces pombe. A different control mechanism operates in Candida utilis to give a damped oscillation after the anaerobic-aerobic transition. The apparent Km values for respiration of the three yeasts were in the range 1.3-1.8 microM-O2. The apparent Km values for O2 of the Pasteur effect were 5 and 13 microM for catabolite-repressed and derepressed S. uvarum respectively and 7 microM for Sch. pombe. These results are discussed with respect to currently accepted mechanisms for the control of glycolysis.

  6. Instrumentation for mass spectrometry: 1997

    Energy Technology Data Exchange (ETDEWEB)

    McLuckey, S.A.

    1997-08-01

    All mass spectrometry experiments involve the manipulation of material, an interface with the mass spectrometer, ionization, ion manipulation/analysis, detection and data collection/reduction. Each of these elements involve instrumentation. The wide range of species now amenable to mass spectrometry and the diverse areas of physical science in which it plays a role have led to a seemingly unlimited array of instrumental combinations. However, only a limited number of mass analyzers, and their combinations, dominate. The dominant analyzers include time-of-flight, Fourier transform ion cyclotron resonance, the Paul trap, the mass filter, and the sector mass spectrometer. Why there are so few (or so many, depending upon one`s point of view) can be understood upon consideration of a set of mass analyzer figures of merit. These include mass resolution, mass accuracy, mass range, dynamic range, abundance sensitivity, precision, efficiency, speed, MS{sup n} capability, compatibility with the ionizer, cost, and size. The most appropriate form of mass spectrometry is determined by the priorities of the particular measurement placed on the various mass analyzer characteristics and the relative strengths of the analyzers in meeting the requirements. Each of the analyzer types has a unique set of figures of merit that makes it optimally suited for particular applications. This paper discusses these figures of merit, provides data illustrating recent developments for each analyzer type, and gives the figures of merit of each type of analyzer as they stand in 1997. 101 refs., 24 figs.

  7. Interlaboratory study of the ion source memory effect in 36Cl accelerator mass spectrometry

    Science.gov (United States)

    Pavetich, Stefan; Akhmadaliev, Shavkat; Arnold, Maurice; Aumaître, Georges; Bourlès, Didier; Buchriegler, Josef; Golser, Robin; Keddadouche, Karim; Martschini, Martin; Merchel, Silke; Rugel, Georg; Steier, Peter

    2014-06-01

    Understanding and minimization of contaminations in the ion source due to cross-contamination and long-term memory effect is one of the key issues for accurate accelerator mass spectrometry (AMS) measurements of volatile elements. The focus of this work is on the investigation of the long-term memory effect for the volatile element chlorine, and the minimization of this effect in the ion source of the Dresden accelerator mass spectrometry facility (DREAMS). For this purpose, one of the two original HVE ion sources at the DREAMS facility was modified, allowing the use of larger sample holders having individual target apertures. Additionally, a more open geometry was used to improve the vacuum level. To evaluate this improvement in comparison to other up-to-date ion sources, an interlaboratory comparison had been initiated. The long-term memory effect of the four Cs sputter ion sources at DREAMS (two sources: original and modified), ASTER (Accélérateur pour les Sciences de la Terre, Environnement, Risques) and VERA (Vienna Environmental Research Accelerator) had been investigated by measuring samples of natural 35Cl/37Cl-ratio and samples highly-enriched in 35Cl (35Cl/37Cl ∼ 999). Besides investigating and comparing the individual levels of long-term memory, recovery time constants could be calculated. The tests show that all four sources suffer from long-term memory, but the modified DREAMS ion source showed the lowest level of contamination. The recovery times of the four ion sources were widely spread between 61 and 1390 s, where the modified DREAMS ion source with values between 156 and 262 s showed the fastest recovery in 80% of the measurements.

  8. Mass Spectrometry Instrumentation in Proteomics

    DEFF Research Database (Denmark)

    Sprenger, Richard Remko; Roepstorff, Peter

    2012-01-01

    Mass spectrometry has evolved into a crucial technology for the field of proteomics, enabling the comprehensive study of proteins in biological systems. Innovative developments have yielded flexible and versatile mass spectrometric tools, including quadrupole time-of-flight, linear ion trap...

  9. Functional genomics by mass spectrometry

    DEFF Research Database (Denmark)

    Andersen, Jens S.; Mann, M

    2000-01-01

    Systematic analysis of the function of genes can take place at the oligonucleotide or protein level. The latter has the advantage of being closest to function, since it is proteins that perform most of the reactions necessary for the cell. For most protein based ('proteomic') approaches to gene...... function, mass spectrometry is the method of choice. Mass spectrometry can now identify proteins with very high sensitivity and medium to high throughput. New instrumentation for the analysis of the proteome has been developed including a MALDI hybrid quadrupole time of flight instrument which combines...... numbers of intact proteins by mass spectrometry directly. Examples from this laboratory illustrate biological problem solving by modern mass spectrometric techniques. These include the analysis of the structure and function of the nucleolus and the analysis of signaling complexes....

  10. Digital Imaging Mass Spectrometry

    CERN Document Server

    Bamberger, Casimir; Bamberger, Andreas

    2011-01-01

    Methods to visualize the two-dimensional distribution of molecules by mass spectrometric imaging evolve rapidly and yield novel applications in biology, medicine, and material surface sciences. Most mass spectrometric imagers acquire high mass resolution spectra spot-by-spot and thereby scan the object's surface. Thus, imaging is slow and image reconstruction remains cumbersome. Here we describe an imaging mass spectrometer that exploits the true imaging capabilities by ion optical means for the time of flight mass separation. The mass spectrometer is equipped with the ASIC Timepix chip as an array detector to acquire the position, mass, and intensity of ions that are imaged by MALDI directly from the target sample onto the detector. This imaging mass spectrometer has a spatial resolving power at the specimen of (84\\pm35) \\mu m with a mass resolution of 45 and locates atoms or organic compounds on a surface area up to ~2 cm2. Extended laser spots of ~5 mm2 on structured specimens allowed parallel imaging of s...

  11. Symposium on accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    None

    1981-01-01

    The area of accelerator mass spectrometry has expanded considerably over the past few years and established itself as an independent and interdisciplinary research field. Three years have passed since the first meeting was held at Rochester. A Symposium on Accelerator Mass Spectrometry was held at Argonne on May 11-13, 1981. In attendance were 96 scientists of whom 26 were from outside the United States. The present proceedings document the program and excitement of the field. Papers are arranged according to the original program. A few papers not presented at the meeting have been added to complete the information on the status of accelerator mass spectrometry. Individual papers were prepared separately for the data base.

  12. Sharp-bounded zones link to the effect in planar chromatography-bioassay-mass spectrometry.

    Science.gov (United States)

    Klingelhöfer, Ines; Morlock, Gertrud E

    2014-09-19

    The traditional direct bioautography workflow was substantially altered to yield narrow, sharp-bounded effective zones. For the first time, microorganisms quantitatively detected the single effective compounds in complex samples, separated in parallel on a planar chromatogram. This novel effect-directed workflow was demonstrated and optimized for the discovery of endocrine disrupting compounds (EDCs) reacting with the human estrogen receptor down to the femtogram-per-zone range, like 250fg/zone for 17β-estradiol (E2). For application volumes of up to 0.5mL, estrogen-effective compounds could directly be detected in complex samples at the ultratrace level (ng/kg-range). Sharp-bounded, estrogen-effective zones discovered were further characterized by direct elution into the mass spectrometer. HPTLC-ESI-MS mass spectra of (xeno)estrogens were shown for the first time. Owed to the substantially improved zone resolution, compound assignment was reliable and a comparison of the receptor affinities was conducted for six (xeno)estrogens. Also, long-term cell cultivation of the genetically modified yeast was demonstrated on the HPTLC plate. The optimized HPTLC-pYES workflow was proven for real food samples, exemplarily shown for beer. The general applicability of generating sharp-bounded zones was successfully proven by transfer of the fundamentally improved workflow to the Bacillus subtilis bioassay used for discovery of antibiotics in plant extracts. This new era of quantitative direct bioautography in combination with mass spectrometry will accelerate the scientific understanding in a wide application field via the streamlined access to fast and reliable information on effective components in complex samples.

  13. Mass spectrometry for biomarker development

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Chaochao; Liu, Tao; Baker, Erin Shammel; Rodland, Karin D.; Smith, Richard D.

    2015-06-19

    Biomarkers potentially play a crucial role in early disease diagnosis, prognosis and targeted therapy. In the past decade, mass spectrometry based proteomics has become increasingly important in biomarker development due to large advances in technology and associated methods. This chapter mainly focuses on the application of broad (e.g. shotgun) proteomics in biomarker discovery and the utility of targeted proteomics in biomarker verification and validation. A range of mass spectrometry methodologies are discussed emphasizing their efficacy in the different stages in biomarker development, with a particular emphasis on blood biomarker development.

  14. Cluster secondary ion mass spectrometry microscope mode mass spectrometry imaging

    NARCIS (Netherlands)

    Kiss, A.; Smith, D.F.; Jungmann, JH; Heeren, R.M.A.

    2013-01-01

    RATIONALE: Microscope mode imaging for secondary ion mass spectrometry is a technique with the promise of simultaneous high spatial resolution and high-speed imaging of biomolecules from complex surfaces. Technological developments such as new position-sensitive detectors, in combination with

  15. Effective representation and storage of mass spectrometry-based proteomic data sets for the scientific community

    DEFF Research Database (Denmark)

    Olsen, Jesper V; Mann, Matthias

    2011-01-01

    Mass spectrometry-based proteomics has emerged as a technology of choice for global analysis of cell signaling networks. However, reporting and sharing of MS data are often haphazard, limiting the usefulness of proteomics to the signaling community. We argue that raw data should always be provided...... mechanisms for community-wide sharing of these data....

  16. Interlaboratory study of the ion source memory effect in {sup 36}Cl accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Pavetich, Stefan, E-mail: s.pavetich@hzdr.de [Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstraße 400, 01314 Dresden (Germany); Akhmadaliev, Shavkat [Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstraße 400, 01314 Dresden (Germany); Arnold, Maurice; Aumaître, Georges; Bourlès, Didier [Aix-Marseille Université, CEREGE CNRS-IRD, F-13545 Aix-en-Provence (France); Buchriegler, Josef [Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstraße 400, 01314 Dresden (Germany); University of Vienna, Faculty of Physics, VERA Laboratory, Währingerstraße 17, 1090 Vienna (Austria); Golser, Robin [University of Vienna, Faculty of Physics, VERA Laboratory, Währingerstraße 17, 1090 Vienna (Austria); Keddadouche, Karim [Aix-Marseille Université, CEREGE CNRS-IRD, F-13545 Aix-en-Provence (France); Martschini, Martin [University of Vienna, Faculty of Physics, VERA Laboratory, Währingerstraße 17, 1090 Vienna (Austria); Merchel, Silke; Rugel, Georg [Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstraße 400, 01314 Dresden (Germany); Steier, Peter [University of Vienna, Faculty of Physics, VERA Laboratory, Währingerstraße 17, 1090 Vienna (Austria)

    2014-06-01

    Highlights: • Long-term memory effect in negative ion sources investigated for chlorine isotopes. • Interlaboratory comparison of four up-to date negative ion sources. • Ion source improvement at DREAMS for minimization of long-term memory effect. • Long-term memory effect is the limitation for precise AMS data of volatile elements. • Findings to be considered for samples with highly variable ratios of {sup 36}Cl/Cl and {sup 129}I/I. - Abstract: Understanding and minimization of contaminations in the ion source due to cross-contamination and long-term memory effect is one of the key issues for accurate accelerator mass spectrometry (AMS) measurements of volatile elements. The focus of this work is on the investigation of the long-term memory effect for the volatile element chlorine, and the minimization of this effect in the ion source of the Dresden accelerator mass spectrometry facility (DREAMS). For this purpose, one of the two original HVE ion sources at the DREAMS facility was modified, allowing the use of larger sample holders having individual target apertures. Additionally, a more open geometry was used to improve the vacuum level. To evaluate this improvement in comparison to other up-to-date ion sources, an interlaboratory comparison had been initiated. The long-term memory effect of the four Cs sputter ion sources at DREAMS (two sources: original and modified), ASTER (Accélérateur pour les Sciences de la Terre, Environnement, Risques) and VERA (Vienna Environmental Research Accelerator) had been investigated by measuring samples of natural {sup 35}Cl/{sup 37}Cl-ratio and samples highly-enriched in {sup 35}Cl ({sup 35}Cl/{sup 37}Cl ∼ 999). Besides investigating and comparing the individual levels of long-term memory, recovery time constants could be calculated. The tests show that all four sources suffer from long-term memory, but the modified DREAMS ion source showed the lowest level of contamination. The recovery times of the four ion

  17. [Mass spectrometry analysis of blood plasma lipidome as method of disease diagnostics, evuation of effectiveness and optimization of drug therapy].

    Science.gov (United States)

    Lokhov, P G; Maslov, D L; Balashova, E E; Trifonova, O P; Medvedeva, N V; Torkhovskaya, T I; Ipatova, O M; Archakov, A I; Malyshev, P P; Kukharchuk, V V; Shestakova, E A; Shestakova, M V; Dedov, I I

    2015-01-01

    A new method for the analysis of blood lipid based on direct mass spectrometry of lipophilic low molecular weight fraction of blood plasma has been considered. Such technique allows quantification of hundreds of various types of lipids and this changes existing concepts on diagnostics of lipid disorders and related diseases. The versatility and quickness of the method significantly simplify its wide use. This method is applicable for diagnostics of atherosclerosis, diabetes, cancer and other diseases. Detalization of plasma lipid composition at the molecular level by means of mass spectrometry allows to assess the effectiveness of therapy and to optimize the drug treatment of cardiovascular diseases by phospholipid preparations.

  18. A mass spectrometry primer for mass spectrometry imaging.

    Science.gov (United States)

    Rubakhin, Stanislav S; Sweedler, Jonathan V

    2010-01-01

    Mass spectrometry imaging (MSI), a rapidly growing subfield of chemical imaging, employs mass spectrometry (MS) technologies to create single- and multi-dimensional localization maps for a variety of atoms and molecules. Complimentary to other imaging approaches, MSI provides high chemical specificity and broad analyte coverage. This powerful analytical toolset is capable of measuring the distribution of many classes of inorganics, metabolites, proteins, and pharmaceuticals in chemically and structurally complex biological specimens in vivo, in vitro, and in situ. The MSI approaches highlighted in this Methods in Molecular Biology volume provide flexibility of detection, characterization, and identification of multiple known and unknown analytes. The goal of this chapter is to introduce investigators who may be unfamiliar with MS to the basic principles of the mass spectrometric approaches as used in MSI. In addition to guidelines for choosing the most suitable MSI method for specific investigations, cross-references are provided to the chapters in this volume that describe the appropriate experimental protocols.

  19. Chemical Ionization Mass Spectrometry.

    Science.gov (United States)

    1980-01-30

    mass spectrometer. Also discussed were Corporation, St. Louis , Mo. unique analytical applications of several negative ion chemical Synthesis of the...were purchsed from obtained at a probe temperature of 180-200 °C and displays Sigma Chemical Co.. St. Louis , Mo. Arginine hydrochloride (4) a M4...13) Rosenstock. H, M.: Drax . K.: Stener. B. W: Hernon J. T. J. Phys. Chem, Ref. Data 1977, 6, Supl. 1. 774-783,167 occur in the ratio of 10/ 1

  20. Effect of the solvent flow rate on the ionization efficiency in atmospheric pressure photoionization-mass spectrometry

    NARCIS (Netherlands)

    Kauppila, TJ; Bruins, AP; Kostiainen, R

    In the novel atmospheric pressure photoionization-mass spectrometry the ionization efficiency has been observed to decrease when the solvent flow rate is increased. The effect of the flow rate on the ionization efficiency was studied by comparing the behavior of two analytes, one of which is ionized

  1. Mass Spectrometry in Polymer Chemistry

    CERN Document Server

    Barner-Kowollik, Christopher; Falkenhagen, Jana; Weidner, Steffen

    2011-01-01

    Combining an up-to-date insight into mass-spectrometric polymer analysis beyond MALDI with application details of the instrumentation, this is a balanced and thorough presentation of the most important and widely used mass-spectrometric methods.Written by the world's most proficient experts in the field, the book focuses on the latest developments, covering such technologies and applications as ionization protocols, tandem and liquid chromatography mass spectrometry, gas-phase ion-separation techniques and automated data processing. Chapters on sample preparation, polymer degradation and the u

  2. Substituent effects on the binding of natural product anthocyanidin inhibitors to influenza neuraminidase with mass spectrometry.

    Science.gov (United States)

    Swaminathan, Kavya; Müller, Patrick; Downard, Kevin M

    2014-05-30

    The binding of three closely related anthocyanins within the 430-cavity of influenza neuraminidase is studied using a combination of mass spectrometry and molecular docking. Despite their similar structures, which differ only in the number and position of the hydroxyl substituents on the phenyl group attached to the chromenylium ring, subtle differences in their binding characteristics are revealed by mass spectrometry and molecular docking that are in accord with their inhibitory properties by neuraminidase inhibition assays. The cyanidin and delphinidin, with the greatest number of hydroxyl groups, bind more strongly and are better inhibitors than pelargonidin that contains a lone hydroxyl group at the 4' position. The study demonstrates, for the first time, the sensitivity of the mass spectrometry based approach for investigating the molecular basis and relative affinity of antiviral inhibitors, with subtly different structures, to their target protein. It has broader application for the screening of other protein interactions more generally with reasonable high-throughput. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Laser sputter neutral mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    King, B.V.; Clarke, M.; Hu, H.; Betz [Newcastle Univ., NSW (Australia). Dept. of Physics

    1993-12-31

    Laser sputter neutral mass spectrometry (LSNMS) is an emerging technique for highly sensitive surface analysis. In this technique a target is bombarded with a pulsed beam of keV ions. The sputtered particles are intercepted by a high intensity pulsed laser beam above the surface and ionised with almost 100% efficiency. The photions may then be mass analysed using a quadrupole or, more commonly, using time of flight (TOF) techniques. In this method photoions are extracted from the ionisation region, accelerated to a known energy E{sub o} and strike a channelplate detector a distance `d` away. The flight time `t` of the photoions is then related to their mass by `d` {radical}m / {radical} 2E{sub o} so measurement of `t` allows mass spectra to be obtained. It is found that LSNMS is an emerging technique of great sensitivity and flexibility, useful for both applied analysis and to investigate basic sputtering processes. 4 refs., 3 figs.

  4. Effects of Temperature and Energy on Stability of Oligomeric Enzyme Probed on Electrospray Ionization Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    LI Zhi-li

    2008-01-01

    Escherichia coli 3-Deoxy-D-manno-octulosonate 8-phosphate(KDO8P) synthase catalyzed the condensation reaction between D-arabinose 5-phosphate(A5P) and phosphoenolpyruvate(PEP) to form KDO8P and inorganic phosphate(P1).The noncovalent tetrameric association of KDO8P synthase was observed and dissociated in gas phase by means of electrospray ionization mass spectrometry under the very "soft" conditions.The results indicate that PEP-bound enzyme generated abundant tetrameric species as well as monomeric species at the "soft" conditions,whereas,the unbound enzyme favored the formation of a dimeric species.The mass spectra of the mixture of the enzyme with one of substrates,PEP,and A5P or one of products,KDO8P and Pi show that the complex of the unbound enzyme with PEP or P1 was prone to the formation of a monomeric species,whereas,that of the unbound enzyme with ASP or KDO8P was similar to the unbound enzyme.The intensity of the dimeric species increased with the increase of temperature at a collision voltage of 10 V.Taken together,the results presented here suggest that mass spectrometry will be a powerful tool to explore subtile conformational changes and/or subunit-subunit interactions of multiprotein assembly induced by ligand-binding and/or the changes of environmental conditions.

  5. Quantitative mass spectrometry: an overview

    Science.gov (United States)

    Urban, Pawel L.

    2016-10-01

    Mass spectrometry (MS) is a mainstream chemical analysis technique in the twenty-first century. It has contributed to numerous discoveries in chemistry, physics and biochemistry. Hundreds of research laboratories scattered all over the world use MS every day to investigate fundamental phenomena on the molecular level. MS is also widely used by industry-especially in drug discovery, quality control and food safety protocols. In some cases, mass spectrometers are indispensable and irreplaceable by any other metrological tools. The uniqueness of MS is due to the fact that it enables direct identification of molecules based on the mass-to-charge ratios as well as fragmentation patterns. Thus, for several decades now, MS has been used in qualitative chemical analysis. To address the pressing need for quantitative molecular measurements, a number of laboratories focused on technological and methodological improvements that could render MS a fully quantitative metrological platform. In this theme issue, the experts working for some of those laboratories share their knowledge and enthusiasm about quantitative MS. I hope this theme issue will benefit readers, and foster fundamental and applied research based on quantitative MS measurements. This article is part of the themed issue 'Quantitative mass spectrometry'.

  6. Electrophoresis-mass spectrometry probe

    Science.gov (United States)

    Andresen, Brian D.; Fought, Eric R.

    1987-01-01

    The invention involves a new technique for the separation of complex mixtures of chemicals, which utilizes a unique interface probe for conventional mass spectrometers which allows the electrophoretically separated compounds to be analyzed in real-time by a mass spectrometer. This new chemical analysis interface, which couples electrophoresis with mass spectrometry, allows complex mixtures to be analyzed very rapidly, with much greater specificity, and with greater sensitivity. The interface or probe provides a means whereby large and/or polar molecules in complex mixtures to be completely characterized. The preferred embodiment of the probe utilizes a double capillary tip which allows the probe tip to be continually wetted by the buffer, which provides for increased heat dissipation, and results in a continually operating interface which is more durable and electronically stable than the illustrated single capillary tip probe interface.

  7. Protein Analysis by Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Cindic, M.

    2008-04-01

    Full Text Available Soft ionization techniques, electrospray (ESI and matrix-assisted laser desorption/ionization (MALDI make the analysis of biomolecules by mass spectrometry (MS possible. MS is used for determination of the molecular weight of peptides and protein, sequence analysis, characterization of protein-ligand interactions etc. The detection limit, resolution and mass accuracy depend on instrument used (Table 1. Impurities (buffers, salts, detergents can reduce the ion intensities or even totally suppress them, so a separation method (chromatography, 2D-gel electrophoresis must be used for purification of the sample.Molecular mass of intact protein can be determined by ESI or MALDI MS. Multiply charged ions are produced by ESI MS, while singly charged ions are predominant in MALDI spectra (Fig. 2.Sequence analysis of proteins by MS can be performed using peptide mass fingerprint. In this method, proteins are separated by 2-D gel electrophoresis and digested with specific protease (Table 2 or digested and then separated by two-dimensional chromatography (Fig. 1. The obtained peptide mixtures are analyzed by MS or MALDI-TOF technique. The masses determined by MS are compared with calculated masses from database entries. Different algorithms have been developed for protein identification. Example of posttranslational modifications (N- and O-glycosylation and protein sequence complex analysis after dual digestion (endoproteinase digestion followed by endoglycosidase digestion is shown in Fig. 3.It is known that detection of peptides by MS is influenced by intrinsic properties like amino acid composition, the basicity of the C-terminal amino acid, hydrophobicity, etc. Arginine-containing peptides dominate in MS spectra of tryptic digest, so the chemical derivatization of lysine terminal residue by O-methilisourea or 2-methoxy-4,5-1H-imidazole was suggested (Fig. 4.The peptide mass fingerprint method can be improved further by peptide fragmentation using tandem

  8. Modeling HER2 effects on cell behavior from mass spectrometry phosphotyrosine data.

    Directory of Open Access Journals (Sweden)

    Neil Kumar

    2007-01-01

    Full Text Available Cellular behavior in response to stimulatory cues is governed by information encoded within a complex intracellular signaling network. An understanding of how phenotype is determined requires the distributed characterization of signaling processes (e.g., phosphorylation states and kinase activities in parallel with measures of resulting cell function. We previously applied quantitative mass spectrometry methods to characterize the dynamics of tyrosine phosphorylation in human mammary epithelial cells with varying human epidermal growth factor receptor 2 (HER2 expression levels after treatment with epidermal growth factor (EGF or heregulin (HRG. We sought to identify potential mechanisms by which changes in tyrosine phosphorylation govern changes in cell migration or proliferation, two behaviors that we measured in the same cell system. Here, we describe the use of a computational linear mapping technique, partial least squares regression (PLSR, to detail and characterize signaling mechanisms responsible for HER2-mediated effects on migration and proliferation. PLSR model analysis via principal component inner products identified phosphotyrosine signals most strongly associated with control of migration and proliferation, as HER2 expression or ligand treatment were individually varied. Inspection of these signals revealed both previously identified and novel pathways that correlate with cell behavior. Furthermore, we isolated elements of the signaling network that differentially give rise to migration and proliferation. Finally, model analysis identified nine especially informative phosphorylation sites on six proteins that recapitulated the predictive capability of the full model. A model based on these nine sites and trained solely on data from a low HER2-expressing cell line a priori predicted migration and proliferation in a HER2-overexpressing cell line. We identify the nine signals as a "network gauge," meaning that when interrogated

  9. Quantitative mass spectrometry: an overview

    Science.gov (United States)

    2016-01-01

    Mass spectrometry (MS) is a mainstream chemical analysis technique in the twenty-first century. It has contributed to numerous discoveries in chemistry, physics and biochemistry. Hundreds of research laboratories scattered all over the world use MS every day to investigate fundamental phenomena on the molecular level. MS is also widely used by industry—especially in drug discovery, quality control and food safety protocols. In some cases, mass spectrometers are indispensable and irreplaceable by any other metrological tools. The uniqueness of MS is due to the fact that it enables direct identification of molecules based on the mass-to-charge ratios as well as fragmentation patterns. Thus, for several decades now, MS has been used in qualitative chemical analysis. To address the pressing need for quantitative molecular measurements, a number of laboratories focused on technological and methodological improvements that could render MS a fully quantitative metrological platform. In this theme issue, the experts working for some of those laboratories share their knowledge and enthusiasm about quantitative MS. I hope this theme issue will benefit readers, and foster fundamental and applied research based on quantitative MS measurements. This article is part of the themed issue ‘Quantitative mass spectrometry’. PMID:27644965

  10. The Effect of Solvent on the Analysis of Secondary Organic Aerosol Using Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Bateman, Adam P. [Univ. of California, Irvine, CA (United States); Walser, Maggie L. [Univ. of California, Irvine, CA (United States); Dessiaterik, Yury [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Laskin, Julia [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Laskin, Alexander [Univ. of California, Irvine, CA (United States); Nizkorodov, Serguei [Univ. of California, Irvine, CA (United States)

    2008-08-29

    Solvent-analyte reactions in organic aerosol (OA) extracts prepared for analysis by electrospray ionization mass spectrometry (ESI-MS) were examined. Secondary organic aerosol (SOA) produced by ozonation of d-limonene as well as several test organic chemicals with functional groups typical for OA constituents were dissolved and stored in methanol, d3-methanol, acetonitrile, and d3-acetonitrile to investigate the extent and relative rates of reactions between analyte and solvent. High resolution ESI-MS showed that reactions of carbonyls with methanol produce significant amounts of hemiacetals and acetals on time scales ranging from several minutes to several days, with the reaction rates increasing in acidified solutions. Carboxylic acid groups were observed to react with methanol resulting in the formation of esters. In contrast, acetonitrile extracts showed no evidence of reactions with analyte molecules, suggesting that acetonitrile is the preferred solvent for SOA extraction. The use of solvent-analyte reactivity as an analytical chemistry tool for the improved characterization of functional groups in complex organic mixtures was also demonstrated. Direct comparison between ESI mass spectra of the same SOA samples extracted in reactive (methanol) versus non-reactive (acetonitrile) solvents was used to estimate the relative fractions of ketones (≥38%), aldehydes (≥6%), and carboxylic acids (≥55%) in d-limonene SOA.

  11. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    Science.gov (United States)

    Rondo, L.; Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-03-01

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

  12. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    CERN Document Server

    Rondo, L.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-01-01

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosolnucleation. Based on quantum chemical calculations it has been suggested that the quantitative detectionof gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased inthe presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was setup at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection ofH2SO4in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time inthe CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF(Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutralsulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presenceof dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS...

  13. Laser-cooling-assisted mass spectrometry

    CERN Document Server

    Schneider, Christian; Chen, Kuang; Sullivan, Scott T; Hudson, Eric R

    2014-01-01

    Mass spectrometry is used in a wide range of scientific disciplines including proteomics, pharmaceutics, forensics, and fundamental physics and chemistry. Given this ubiquity, there is a worldwide effort to improve the efficiency and resolution of mass spectrometers. However, the performance of all techniques is ultimately limited by the initial phase-space distribution of the molecules being analyzed. Here, we dramatically reduce the width of this initial phase-space distribution by sympathetically cooling the input molecules with laser-cooled, co-trapped atomic ions, improving both the mass resolution and detection efficiency of a time-of-flight mass spectrometer by over an order of magnitude. Detailed molecular dynamics simulations verify the technique and aid with evaluating its effectiveness. Our technique appears to be applicable to other types of mass spectrometers.

  14. Laser-Cooling-Assisted Mass Spectrometry

    Science.gov (United States)

    Schneider, Christian; Schowalter, Steven J.; Chen, Kuang; Sullivan, Scott T.; Hudson, Eric R.

    2014-09-01

    Mass spectrometry is used in a wide range of scientific disciplines including proteomics, pharmaceutics, forensics, and fundamental physics and chemistry. Given this ubiquity, there is a worldwide effort to improve the efficiency and resolution of mass spectrometers. However, the performance of all techniques is ultimately limited by the initial phase-space distribution of the molecules being analyzed. Here, we dramatically reduce the width of this initial phase-space distribution by sympathetically cooling the input molecules with laser-cooled, cotrapped atomic ions, improving both the mass resolution and detection efficiency of a time-of-flight mass spectrometer by over an order of magnitude. Detailed molecular-dynamics simulations verify the technique and aid with evaluating its effectiveness. This technique appears to be applicable to other types of mass spectrometers.

  15. Matrix-assisted laser desorption ion trap mass spectrometry: efficient isolation and effective fragmentation of peptide ions.

    Science.gov (United States)

    Qin, J; Chait, B T

    1996-07-01

    Effective analysis of the sequence of peptides using matrix-assisted laser desorption/ionization (MALDI) tandem ion trap mass spectrometry requires efficient mass isolation and the ability to induce extensive sequence-specific fragmentation. The present paper describes a new excitation scheme, which we term red-shifted off-resonance large-amplitude excitation (RSORLAE), that can deposit higher amounts of internal energy in ions than is feasible with conventional resonant excitation. The new method provides an effective means for inducing fragmentation of MALDI-produced peptide ions with m/z values up to 3500. Prior to excitation, it is necessary to isolate ions of interest with high efficiency. We demonstrate that isolation efficiencies of > 95% can be achieved by careful design of the rf scan functions used during ion isolation. In particular, sudden transitions in the amplitude of the rf field (from low to high amplitudes) must be avoided. The combined improvements in the efficiency for ion isolation and the efficacy of ion activation make MALDI tandem ion trap mass spectrometry a practical tool for the characterization of proteins with high sensitivity.

  16. NICHD Biomedical Mass Spectrometry Core Facility

    Data.gov (United States)

    Federal Laboratory Consortium — The NICHD Biomedical Mass Spectrometry Core Facility was created under the auspices of the Office of the Scientific Director to provide high-end mass-spectrometric...

  17. Chemical Analysis of Astragali Complanati Semen and Its Hypocholesterolemic Effect Using Serum Metabolomics Based on Gas Chromatography-Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Tung Ting Sham

    2017-07-01

    Full Text Available The hypocholesterolemic protective effect of the dried seed of Astragalus complanatus (ACS was investigated in rats fed with normal diet, high cholesterol diet (HCD, and HCD plus 70% ethanol extract of ACS (600 mg/kg/day by oral gavage for four weeks. ACS extract was tested to be rich in antioxidants, which may be contributed to its high content of phenolic compounds. Consumption of ACS remarkably suppressed the elevated total cholesterol (p < 0.01 and LDL-C (p < 0.001 induced by HCD. Chemical constituents of ACS extract were analyzed by ultra-performance liquid chromatography coupled with electrospray ionization orbitrap mass spectrometry and the results showed that the ACS extract mainly consisted of phenolic compounds including flavonoids and flavonoid glycosides. In addition, based on the serum fatty acid profiles, elucidated using gas chromatography-mass spectrometry, free and esterified fatty acids including docosapentaenoic acid, adrenic acid, dihomo-γ-linolenic acid and arachidonic acid were regulated in ACS treatment group. Western blot results further indicated the protein expression of peroxisome proliferator-activated receptor alpha (PPARα (p < 0.05 in liver was upregulated in ACS treatment group. To conclude, our results clearly demonstrated that ACS provides beneficial effect on lowering HCD associated detrimental change.

  18. Aerosol MALDI mass spectrometry for bioaerosol analysis

    NARCIS (Netherlands)

    Kleefsman, W.A.

    2008-01-01

    In the thesis Aerosol MALDI mass spectrometry for bioaerosol analysis is described how the aerosol mass spectrometer of the TU Delft has been further developed for the on-line analysis of bioaerosols. Due to the implemented improvements mass spectra with high resolution and a high mass range can be

  19. Absorption Mode FTICR Mass Spectrometry Imaging

    NARCIS (Netherlands)

    Smith, D.F.; Kilgour, D.P.A.; Konijnenburg, M.; O'Connor, P.B.; Heeren, R.M.A.

    2013-01-01

    Fourier transform ion cyclotron resonance mass spectrometry offers the highest mass resolving power for molecular imaging experiments. This high mass resolving power ensures that closely spaced peaks at the same nominal mass are resolved for proper image generation. Typically higher magnetic fields

  20. Effect of ginseng polysaccharide on the urinary excretion of type 2 diabetic rats studied by liquid chromatography-mass spectrometry.

    Science.gov (United States)

    Niu, Jun; Pi, Zifeng; Yue, Hao; Wang, Yang; Yu, Qing; Liu, Shuying

    2012-10-15

    Ginseng polysaccharide is known to have anti-hyperglycemic and anti-hyperlipidemic effects in vivo and its precise mechanism of action is not clear. A urinary metabolomics method based on rapid-resolution liquid chromatography/mass spectrometry (RRLC/MS) was developed to investigate the effect of water-soluble ginseng polysaccharide (WGP) on type 2 diabetes in rats. Principal component analysis (PCA) was carried out for pattern recognition and a clear separation between type 2 diabetic rats and those treated with WGP was achieved. Eight potential biomarkers were found and identified. Significantly increased inosine, serotonin, phenylpropionylglycine and dodecanedioic acid showed the effect of WGP on purine metabolism, tryptophan metabolism, fatty acid metabolism and energy metabolism. 1-Methyladenine, 4-deoxyerythronic acid, 5-hydroxyhexanoic acid and tetrahydrocortisol were significantly decreased which indicated that WGP can regulate DNA metabolism, organic acids metabolism and steroid hormone metabolism. This work is helpful in the effect mechanism study of ginseng polysaccharide.

  1. Zero voltage mass spectrometry probes and systems

    Energy Technology Data Exchange (ETDEWEB)

    Cooks, Robert Graham; Wleklinski, Michael Stanley; Bag, Soumabha; Li, Yafeng

    2017-10-10

    The invention generally relates to zero volt mass spectrometry probes and systems. In certain embodiments, the invention provides a system including a mass spectrometry probe including a porous material, and a mass spectrometer (bench-top or miniature mass spectrometer). The system operates without an application of voltage to the probe. In certain embodiments, the probe is oriented such that a distal end faces an inlet of the mass spectrometer. In other embodiments, the distal end of the probe is 5 mm or less from an inlet of the mass spectrometer.

  2. Biological accelerator mass spectrometry at Uppsala University.

    Science.gov (United States)

    Salehpour, Mehran; Possnert, Göran; Bryhni, Helge; Palminger-Hallén, Ira; Ståhle, Lars

    2009-03-01

    A new research programme for the biological applications of accelerator mass spectrometry has been initiated at Uppsala University and the first results are presented. A (14)C-labelled pharmaceutical substance has been dissolved in human blood, plasma and urine and diluted over 3 orders of magnitude. The measured drug concentrations were found to be in good agreement with the predicted values. Furthermore, the effect of the sample preparation background contribution has been studied as the sample amount was varied down to sub-microl sizes.

  3. Reduction of matrix effects in polystyrene/poly(methylene methacrylate) blends by metal-assisted secondary ion mass spectrometry.

    Science.gov (United States)

    Becker, Nora; Wirtz, Tom

    2012-07-17

    Secondary ion mass spectrometry (SIMS) is a very surface sensitive analysis technique with low detection limits. The main drawback of SIMS is its inherent incapability of providing quantitative information about sample compositions due to the frequent occurrence of ionization- and sputter-induced matrix effects. Metal-assisted SIMS (MetA-SIMS) is an experimental approach that consists in covering an organic sample with a minute amount of a noble metal prior to a static SIMS analysis, the main objective being an increase of the characteristic secondary ion intensities. We show in this article that MetA-SIMS is also a simple and efficient tool for reducing matrix effects in a set of polymer blend samples containing different relative concentrations polystyrene (PS) and poly(methylene methacrylate) (PMMA). These findings can be explained by diffusion processes leading to a sample surface configuration consisting of individual polymer chains embedded in a common Ag matrix.

  4. Gas Chromatography Mass Spectrometry of Quassia undulata Seed ...

    African Journals Online (AJOL)

    Prof. Ogunji

    ... fatty acid methyl ester analysis. Gas chromatography (GC) and mass spectrometry (MS) has proved an effective ... extensive qualitative and quantitative research on the fatty ... chemical properties of biodiesel and other derivatives of fatty ...

  5. Introduction to mass spectrometry-based proteomics

    DEFF Research Database (Denmark)

    Matthiesen, Rune; Bunkenborg, Jakob

    2013-01-01

    Mass spectrometry has been widely applied to study biomolecules and one rapidly developing field is the global analysis of proteins, proteomics. Understanding and handling mass spectrometry data is a multifaceted task that requires many decisions to be made to get the most comprehensive information...... from an experiment. Later chapters in this book deal in-depth with various aspects of the process and how different tools can be applied to the many analytical challenges. This introductory chapter is intended as a basic introduction to mass spectrometry (MS)-based proteomics to set the scene...... for newcomers and give pointers to reference material. There are many applications of mass spectrometry in proteomics and each application is associated with some analytical choices, instrumental limitations and data processing steps that depend on the aim of the study and means of conducting it. Different...

  6. Pyrolysis - gas chromatography - mass spectrometry of lignins

    Energy Technology Data Exchange (ETDEWEB)

    Martin, F.; Saiz-Jimenez, C.; Gonzalez-Vila, F.J.

    1979-01-01

    Milled wood lignins from spruce, beech and bamboo were pyrolysed. The high-boiling products of pyrolysis were studied by GLC and mass spectrometry. The forty-three products identified provide information on the structural units of lignin.

  7. Mass spectrometry of fluorocarbon-labeled glycosphingolipids

    DEFF Research Database (Denmark)

    Li, Yunsen; Arigi, Emma; Eichert, Heather;

    2010-01-01

    A method for generation of novel fluorocarbon derivatives of glycosphingolipids (GSLs) with high affinity for fluorocarbon phases has been developed, and their potential applications to mass spectrometry (MS)-based methodologies for glycosphingolipidomics have been investigated. Sphingolipid...

  8. Imaging mass spectrometry of polymeric materials

    NARCIS (Netherlands)

    Klerk, L.A.

    2009-01-01

    Imaging mass spectrometry (MS) is a technique that makes images of molecular distributions at surfaces based on mass spectral information. At a range (typically a raster) of positions, mass spectra are measured from the surface giving a characteristic fingerprint for the material that is present at

  9. Neutral particle Mass Spectrometry with Nanomechanical Systems

    CERN Document Server

    Sage, Eric; Alava, Thomas; Morel, Robert; Dupré, Cécilia; Hanay, Mehmet Selim; Duraffourg, Laurent; Masselon, Christophe; Hentz, Sébastien

    2014-01-01

    Current approaches to Mass Spectrometry (MS) necessarily rely on the ionization of the analytes of interest and subsequent spectrum interpretation is based on the mass-to-charge ratios of the ions. The resulting charge state distribution can be very complex for high-mass species which may hinder correct interpretation. A new form of MS analysis based on Nano-Electro-Mechanical Systems (NEMS) was recently demonstrated with high-mass ions. Thanks to a dedicated setup comprising both conventional time-of-flight MS (TOF-MS) and NEMS-MS in-situ, we show here for the first time that NEMS-MS analysis is insensitive to charge state: it provides one single peak regardless of the species charge state, highlighting effective clarification over existing MS analysis. All charged particles were thereafter removed from the beam electrostatically, and unlike TOF-MS, NEMS-MS retained its ability to perform mass measurements. This constitutes the first unequivocal measurement of mass spectra of neutral particles. This ability ...

  10. Elemental Composition Analysis to Investigate NOx Effects on Secondary Organic Aerosol from α-Pinene Using Ultrahigh Resolution Mass Spectrometry

    Science.gov (United States)

    Lim, H. J.; Park, J. H.; Babar, Z.

    2015-12-01

    Secondary organic aerosol (SOA) accounts for 20-70% of atmospheric fine aerosol. NOx plays crucial roles in SOA formation and consequently affects the composition and yield of SOA. SOA component speciation is incomplete due to its complex composition of polar oxygenated and multifunctional species. In this study, ultrahigh resolution mass spectrometry (UHR MS) was applied to improve the understanding of NOx effects on biogenic SOA formation by identifying the elemental composition of SOA. Additional research aim was to investigate oligomer components that are considered as a driving force for SOA formation and growth. In this study α-pinene SOA from photochemical reaction was examined. SOA formation was performed in the absence and presence of NOx at dry condition (government (MEST) (No. 2011-01350000).

  11. Ortho effect in electron ionization mass spectrometry of N-acylanilines bearing a proximal halo substituent.

    Science.gov (United States)

    Jariwala, Freneil B; Figus, Margaret; Attygalle, Athula B

    2008-08-01

    Electron ionization (EI) mass spectra are not very helpful for characterizing ortho, meta, and para isomers of underivatized haloanilines since their spectra are virtually identical. In contrast, when the amino group of chloro-, bromo-, or iodoanilines is transformed to an N-formyl, N-acetyl, or N-benzoyl derivative, the spectra of the derivatives reveal a highly dramatic loss of a halogen radical, instead of an HX elimination usually expected from an "ortho effect." For example, the spectra of N-formyl, N-acetyl, and N-benzoyl derivatives of ortho isomers of chloro-, bromo-, and iodoanilines show a very prominent peak at m/z 120, 134, and 196, respectively, for the loss of the corresponding halogen atom.

  12. Matrix effect in the analysis of drugs of abuse from urine with desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS) and desorption electrospray ionization-mass spectrometry (DESI-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Suni, Niina M.; Lindfors, Pia; Laine, Olli [Division of Pharmaceutical Chemistry, University of Helsinki, P.O. Box 56, Helsinki FI-00014 (Finland); Ostman, Pekka; Ojanperae, Ilkka [Hjelt Institute, Department of Forensic Medicine, University of Helsinki, P.O. Box 40, Helsinki FI-00014 (Finland); Kotiaho, Tapio [Division of Pharmaceutical Chemistry, University of Helsinki, P.O. Box 56, Helsinki FI-00014 (Finland); Laboratory of Analytical Chemistry, Department of Chemistry, University of Helsinki, P.O. Box 55, Helsinki FI-00014 (Finland); Kauppila, Tiina J. [Division of Pharmaceutical Chemistry, University of Helsinki, P.O. Box 56, Helsinki FI-00014 (Finland); Kostiainen, Risto, E-mail: risto.kostiainen@helsinki.fi [Division of Pharmaceutical Chemistry, University of Helsinki, P.O. Box 56, Helsinki FI-00014 (Finland)

    2011-08-05

    Highlights: {yields} DAPPI-MS and DESI-MSI in the analysis of drugs of abuse from urine. {yields} DAPPI-MS has better urine matrix tolerance over DESI-MS. {yields} Urine matrix can affect the ionization mechanism in DAPPI. {yields} DAPPI-MS/MS can be used for screening of drugs from urine after sample pretreatment. - Abstract: We have studied the matrix effect within direct analysis of benzodiazepines and opioids from urine with desorption electrospray ionization-mass spectrometry (DESI-MS) and desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS). The urine matrix was found to affect the ionization mechanism of the opioids in DAPPI-MS favoring proton transfer over charge exchange reaction. The sensitivity for the drugs in solvent matrix was at the same level with DESI-MS and DAPPI-MS (LODs 0.05-6 {mu}g mL{sup -1}) but the decrease in sensitivity due to the urine matrix was higher with DESI (typically 20-160-fold) than with DAPPI (typically 2-15-fold) indicating better matrix tolerance of DAPPI over DESI. Also in MS/MS mode, DAPPI provided better sensitivity than DESI for the drugs in urine. The feasibility of DAPPI-MS/MS was then studied in screening the same drugs from five authentic, forensic post mortem urine samples. A reference measurement with gas chromatography-mass spectrometry (GC-MS) (including pretreatment) revealed 16 findings from the samples, whereas with DAPPI-MS/MS after sample pretreatment, 15 findings were made. Sample pretreatment was found necessary, since only eight findings were made from the same samples untreated.

  13. Cluster SIMS Microscope Mode Mass Spectrometry Imaging

    CERN Document Server

    Kiss, András; Jungmann, Julia H; Heeren, Ron M A

    2013-01-01

    Microscope mode imaging for secondary ion mass spectrometry is a technique with the promise of simultaneous high spatial resolution and high speed imaging of biomolecules from complex surfaces. Technological developments such as new position-sensitive detectors, in combination with polyatomic primary ion sources, are required to exploit the full potential of microscope mode mass spectrometry imaging, i.e. to efficiently push the limits of ultra-high spatial resolution, sample throughput and sensitivity. In this work, a C60 primary source is combined with a commercial mass microscope for microscope mode secondary ion mass spectrometry imaging. The detector setup is a pixelated detector from the Medipix/Timepix family with high-voltage post-acceleration capabilities. The mass spectral and imaging performance of the system is tested with various benchmark samples and thin tissue sections. We show that the high secondary ion yield (with respect to traditional monatomic primary ion sources) of the C60 primary ion ...

  14. Aspects of matrix effects in applications of liquid chromatography-mass spectrometry to forensic and clinical toxicology--a review.

    Science.gov (United States)

    Peters, Frank T; Remane, Daniela

    2012-06-01

    In the last decade, liquid chromatography coupled to (tandem) mass spectrometry (LC-MS(-MS)) has become a versatile technique with many routine applications in clinical and forensic toxicology. However, it is well-known that ionization in LC-MS(-MS) is prone to so-called matrix effects, i.e., alteration in response due to the presence of co-eluting compounds that may increase (ion enhancement) or reduce (ion suppression) ionization of the analyte. Since the first reports on such matrix effects, numerous papers have been published on this matter and the subject has been reviewed several times. However, none of the existing reviews has specifically addressed aspects of matrix effects of particular interest and relevance to clinical and forensic toxicology, for example matrix effects in methods for multi-analyte or systematic toxicological analysis or matrix effects in (alternative) matrices almost exclusively analyzed in clinical and forensic toxicology, for example meconium, hair, oral fluid, or decomposed samples in postmortem toxicology. This review article will therefore focus on these issues, critically discussing experiments and results of matrix effects in LC-MS(-MS) applications in clinical and forensic toxicology. Moreover, it provides guidance on performance of studies on matrix effects in LC-MS(-MS) procedures in systematic toxicological analysis and postmortem toxicology.

  15. Theoretical Study of the Sensitivity-Improvement Effect of Phosphoryl Group in Mass Spectrometry of Small Peptides

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    It was found that phosphorylation of small peptide could improve the sensitivity in mass spectrometry. Density functional theory calculations showed that the energy for the protonation of N-(O, O′-dimethyl) phosphoryl glycylglycine is lower than that of glycylglycine. These could help to understanding the experimental results.

  16. Mass Spectrometry of Human Leukocyte Antigen Class I Peptidomes Reveals Strong Effects of Protein Abundance and Turnover on Antigen Presentation

    DEFF Research Database (Denmark)

    Bassani-Sternberg, Michal; Pletscher-Frankild, Sune; Jensen, Lars Juhl

    2015-01-01

    HLA class I molecules reflect the health state of cells to cytotoxic T cells by presenting a repertoire of endogenously derived peptides. However, the extent to which the proteome shapes the peptidome is still largely unknown. Here we present a high-throughput mass-spectrometry-based workflow tha...

  17. Mass Spectrometry in Organic Synthesis: Claisen-Schmidt Base-Catalyzed Condensation and Hammett Correlation of Substituent Effects

    Science.gov (United States)

    Bain, Ryan M.; Pulliam, Christopher J.; Yan, Xin; Moore, Kassandra F.; Mu¨ller, Thomas; Cooks, R. Graham

    2014-01-01

    Undergraduate laboratories generally teach an understanding of chemical reactivity using bulk or semimicroscale experiments with product isolation and subsequent chemical and spectroscopic analysis. In this study students were exposed to mass spectrometry as a means of chemical synthesis as well as analysis. The ionization method used, paper…

  18. Mass Spectrometry in Organic Synthesis: Claisen-Schmidt Base-Catalyzed Condensation and Hammett Correlation of Substituent Effects

    Science.gov (United States)

    Bain, Ryan M.; Pulliam, Christopher J.; Yan, Xin; Moore, Kassandra F.; Mu¨ller, Thomas; Cooks, R. Graham

    2014-01-01

    Undergraduate laboratories generally teach an understanding of chemical reactivity using bulk or semimicroscale experiments with product isolation and subsequent chemical and spectroscopic analysis. In this study students were exposed to mass spectrometry as a means of chemical synthesis as well as analysis. The ionization method used, paper…

  19. Analysis of mass spectrometry data in proteomics

    DEFF Research Database (Denmark)

    Matthiesen, Rune; Jensen, Ole N

    2008-01-01

    that in turn allow protein identification, annotation of secondary modifications, and determination of the absolute or relative abundance of individual proteins. Advances in mass spectrometry-driven proteomics rely on robust bioinformatics tools that enable large-scale data analysis. This chapter describes......The systematic study of proteins and protein networks, that is, proteomics, calls for qualitative and quantitative analysis of proteins and peptides. Mass spectrometry (MS) is a key analytical technology in current proteomics and modern mass spectrometers generate large amounts of high-quality data...... some of the basic concepts and current approaches to the analysis of MS and MS/MS data in proteomics....

  20. A REVIEW ON MASS SPECTROMETRY DETECTORS

    Directory of Open Access Journals (Sweden)

    Khatri Neetu

    2012-10-01

    Full Text Available Mass spectrometry is an analytical technique for "weighing" molecules. Obviously, this is not done with a conventional scale or balance. Instead, mass spectrometry is based upon the principle of the motion of a charged particle that is called an ion, in an electric or magnetic field. The mass to charge ratio (m/z of the ion affects particles motion. Since the charge of an electron is known, the mass to charge ratio (m/z is a measurement of mass of an ion. Mass spectrometry research focuses on the formation of gas phase ions, and detection of ions. Detectors in mass spectrometer detect the separated ions according to m/z ratio. The main disadvantages of conventional detectors are very low sensitivity and poor detection efficiency. Detectors are of a great interest to a wide range of industrial, military, environmental and even biological applications. In recent developments, molecules of higher mass can also be detected and enhanced lifetime under the less than ideal environments typically encountered in mass spectrometers. This review deals in detail about the design, working and principle of mass spectrometric detectors and their recent developments.

  1. Linear electric field mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    McComas, D.J.; Nordholt, J.E.

    1991-03-29

    A mass spectrometer is described having a low weight and low power requirement, for use in space. It can be used to analyze the ionized particles in the region of the spacecraft on which it is mounted. High mass resolution measurements are made by timing ions moving through a gridless cylindrically sysmetric linear electric field.

  2. Matrix effects of calcium on high-precision sulfur isotope measurement by multiple-collector inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Liu, Chenhui; Bian, Xiao-Peng; Yang, Tao; Lin, An-Jun; Jiang, Shao-Yong

    2016-05-01

    Multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has been successfully applied in the rapid and high-precision measurement for sulfur isotope ratios in recent years. During the measurement, the presence of matrix elements would affect the instrumental mass bias for sulfur and these matrix-induced effects have aroused a lot of researchers' interest. However, these studies have placed more weight on highlighting the necessity for their proposed correction protocols (e.g., chemical purification and matrix-matching) while less attention on the key property of the matrix element gives rise to the matrix effects. In this study, four groups of sulfate solutions, which have different concentrations of sulfur (0.05-0.60mM) but a constant sequence of atomic calcium/sulfur ratios (0.1-50), are investigated under wet (solution) and dry (desolvation) plasma conditions to make a detailed evaluation on the matrix effects from calcium on sulfur isotope measurement. Based on a series of comparative analyses, we indicated that, the matrix effects of calcium on both measured sulfur isotope ratios and detected (32)S signal intensities are dependent mainly on the absolute calcium concentration rather than its relative concentration ratio to sulfur (i.e., atomic calcium/sulfur ratio). Also, for the same group of samples, the matrix effects of calcium under dry plasma condition are much more significant than that of wet plasma. This research affords the opportunity to realize direct and relatively precise sulfur isotope measurement for evaporite gypsum, and further provides some suggestions with regard to sulfur isotope analytical protocols for sedimentary pore water.

  3. Gas Chromatography-Mass Spectrometry Analysis of Ulva fasciata (Green Seaweed Extract and Evaluation of Its Cytoprotective and Antigenotoxic Effects

    Directory of Open Access Journals (Sweden)

    Idania Rodeiro

    2015-01-01

    Full Text Available The chemical composition and biological properties of Ulva fasciata aqueous-ethanolic extract were examined. Five components were identified in one fraction prepared from the extract by gas chromatography-mass spectrometry, and palmitic acid and its ethyl ester accounted for 76% of the total identified components. Furthermore, we assessed the extract’s antioxidant properties by using the DPPH, ABTS, and lipid peroxidation assays and found that the extract had a moderate scavenging effect. In an experiment involving preexposition and coexposition of the extract (1–500 µg/mL and benzo[a]pyrene (BP, the extract was found to be nontoxic to C9 cells in culture and to inhibit the cytotoxicity induced by BP. As BP is biotransformed by CYP1A and CYP2B subfamilies, we explored the possible interaction of the extract with these enzymes. The extract (25–50 µg/mL inhibited CYP1A1 activity in rat liver microsomes. Analysis of the inhibition kinetics revealed a mixed-type inhibitory effect on CYP1A1 supersome. The effects of the extract on BP-induced DNA damage and hepatic CYP activity in mice were also investigated. Micronuclei induction by BP and liver CYP1A1/2 activities significantly decreased in animals treated with the extract. The results suggest that Ulva fasciata aqueous-ethanolic extract inhibits BP bioactivation and it may be a potential chemopreventive agent.

  4. Gas Chromatography-Mass Spectrometry Analysis of Ulva fasciata (Green Seaweed) Extract and Evaluation of Its Cytoprotective and Antigenotoxic Effects.

    Science.gov (United States)

    Rodeiro, Idania; Olguín, Sitlali; Santes, Rebeca; Herrera, José A; Pérez, Carlos L; Mangas, Raisa; Hernández, Yasnay; Fernández, Gisselle; Hernández, Ivones; Hernández-Ojeda, Sandra; Camacho-Carranza, Rafael; Valencia-Olvera, Ana; Espinosa-Aguirre, Jesús Javier

    2015-01-01

    The chemical composition and biological properties of Ulva fasciata aqueous-ethanolic extract were examined. Five components were identified in one fraction prepared from the extract by gas chromatography-mass spectrometry, and palmitic acid and its ethyl ester accounted for 76% of the total identified components. Furthermore, we assessed the extract's antioxidant properties by using the DPPH, ABTS, and lipid peroxidation assays and found that the extract had a moderate scavenging effect. In an experiment involving preexposition and coexposition of the extract (1-500 µg/mL) and benzo[a]pyrene (BP), the extract was found to be nontoxic to C9 cells in culture and to inhibit the cytotoxicity induced by BP. As BP is biotransformed by CYP1A and CYP2B subfamilies, we explored the possible interaction of the extract with these enzymes. The extract (25-50 µg/mL) inhibited CYP1A1 activity in rat liver microsomes. Analysis of the inhibition kinetics revealed a mixed-type inhibitory effect on CYP1A1 supersome. The effects of the extract on BP-induced DNA damage and hepatic CYP activity in mice were also investigated. Micronuclei induction by BP and liver CYP1A1/2 activities significantly decreased in animals treated with the extract. The results suggest that Ulva fasciata aqueous-ethanolic extract inhibits BP bioactivation and it may be a potential chemopreventive agent.

  5. Gas Chromatography-Mass Spectrometry Analysis of Ulva fasciata (Green Seaweed) Extract and Evaluation of Its Cytoprotective and Antigenotoxic Effects

    Science.gov (United States)

    Rodeiro, Idania; Olguín, Sitlali; Santes, Rebeca; Herrera, José A.; Pérez, Carlos L.; Mangas, Raisa; Hernández, Yasnay; Fernández, Gisselle; Hernández, Ivones; Hernández-Ojeda, Sandra; Camacho-Carranza, Rafael; Valencia-Olvera, Ana; Espinosa-Aguirre, Jesús Javier

    2015-01-01

    The chemical composition and biological properties of Ulva fasciata aqueous-ethanolic extract were examined. Five components were identified in one fraction prepared from the extract by gas chromatography-mass spectrometry, and palmitic acid and its ethyl ester accounted for 76% of the total identified components. Furthermore, we assessed the extract's antioxidant properties by using the DPPH, ABTS, and lipid peroxidation assays and found that the extract had a moderate scavenging effect. In an experiment involving preexposition and coexposition of the extract (1–500 µg/mL) and benzo[a]pyrene (BP), the extract was found to be nontoxic to C9 cells in culture and to inhibit the cytotoxicity induced by BP. As BP is biotransformed by CYP1A and CYP2B subfamilies, we explored the possible interaction of the extract with these enzymes. The extract (25–50 µg/mL) inhibited CYP1A1 activity in rat liver microsomes. Analysis of the inhibition kinetics revealed a mixed-type inhibitory effect on CYP1A1 supersome. The effects of the extract on BP-induced DNA damage and hepatic CYP activity in mice were also investigated. Micronuclei induction by BP and liver CYP1A1/2 activities significantly decreased in animals treated with the extract. The results suggest that Ulva fasciata aqueous-ethanolic extract inhibits BP bioactivation and it may be a potential chemopreventive agent. PMID:26612994

  6. Characterization of Synthetic Peptides by Mass Spectrometry

    DEFF Research Database (Denmark)

    Prabhala, Bala K; Mirza, Osman; Højrup, Peter;

    2015-01-01

    Mass spectrometry (MS) is well suited for analysis of the identity and purity of synthetic peptides. The sequence of a synthetic peptide is most often known, so the analysis is mainly used to confirm the identity and purity of the peptide. Here, simple procedures are described for MALDI-TOF-MS an......Mass spectrometry (MS) is well suited for analysis of the identity and purity of synthetic peptides. The sequence of a synthetic peptide is most often known, so the analysis is mainly used to confirm the identity and purity of the peptide. Here, simple procedures are described for MALDI...

  7. Human sports drug testing by mass spectrometry.

    Science.gov (United States)

    Schänzer, Wilhelm; Thevis, Mario

    2017-01-01

    Since the installation of anti-doping rules and regulations and their international enforcement in the mid-1960s, mass spectrometry has been an integral part of doping control procedures. Although its utility was limited in the first decade, instrumental improvements and method optimizations have made mass spectrometry, in all its facets, an indispensable tool in modern sports drug testing. In this review, milestones in doping control analysis accomplished in Germany and reaching from the early developments to the current use of hyphenated mass spectrometric techniques concerning low- and high molecular mass analytes are presented. The considered drug classes include anabolic agents, peptidic drugs, nucleotide-derived therapeutics, approved and non-approved organic as well as inorganic analytes, and particular focus is put on drug class- and instrument-driven strategies. © 2015 Wiley Periodicals, Inc. Mass Spec Rev 36:16-46, 2017.

  8. Determination of microcystin-LR in drinking water using UPLC tandem mass spectrometry-matrix effects and measurement.

    Science.gov (United States)

    Li, Wei; Duan, Jinming; Niu, Chaoying; Qiang, Naichen; Mulcahy, Dennis

    2011-10-01

    A simple detection method using ultra-performance liquid chromatography electrospray ionisation tandem mass spectrometry (UPLC-ESI-MS-MS) coupled with the sample dilution method for determining trace microcystin-LR (MC-LR) in drinking water is presented. The limit of detection (LOD) was 0.04 µg/L and the limit of quantitation (LOQ) was 0.1 µg/L. Water matrix effects of ionic strength, dissolved organic carbon (DOC) and pH were examined. The results indicate that signal detection intensity for MC-LR was significantly suppressed as the ionic strength increased from ultrapure water condition, whereas it increased slightly with solution pH and DOC at low concentrations. However, addition of methanol (MeOH) into the sample was able to counter the signal suppression effects. In this study, dilution of the tap water sample by adding 4% MeOH (v/v) was observed to be adequate to compensate for the signal suppression. The recoveries of the samples fortified with MC-LR (0.2, 1, and 10 µg/L) for three different tap water samples ranged from 84.4% to 112.9%.

  9. Effect of piperine on pharmacokinetics of sodium valproate in plasma samples of rats using gas chromatography-mass spectrometry method

    Directory of Open Access Journals (Sweden)

    Bushra Parveen

    2015-01-01

    Full Text Available Piperine (PIP is used as anticonvulsant in traditional Chinese medicine. Co-administration of low-dose sodium valproate with PIP has been regarded to have potential anticonvulsant activity. Aim: This study was intended to investigate the effect of PIP on the pharmacokinetics of sodium valproate (SVP in the plasma samples of rats using gas chromatography-mass spectrometry (GC-MS method. Materials and Methods: The plasma samples obtained after oral administration of SVP, 150 mg/kg and SVP, 150 mg/kg + PIP, and 5 mg/kg to male Wistar rats were used to quantify the concentrations in plasma using GC-MS method. Results: A simple and accurate method developed in-house was applied for the analysis of plasma samples of Wistar rats after oral administration of SVP and PIP + sodium valproate, respectively. The pharmacokinetic parameters reported 14.8-fold increase in plasma concentration (maximum observed concentration in the concentration-time profile, 4.6-fold increase in area under the curve and slightly prolonged time to reach that concentration (1 h of SVP in presence of PIP. Conclusion: The study reaffirms the bioenhancing effect of PIP suggesting possibility of dose reduction of SVP while co-adminstering with PIP.

  10. The Effect of Detergent, Temperature, and Lipid on the Oligomeric State of MscL Constructs: Insights from Mass Spectrometry.

    Science.gov (United States)

    Reading, Eamonn; Walton, Troy A; Liko, Idlir; Marty, Michael T; Laganowsky, Arthur; Rees, Douglas C; Robinson, Carol V

    2015-05-21

    The mechanosensitive channel of large conductance (MscL) acts as an emergency release valve for osmotic shock of bacteria preventing cell lysis. The large pore size, essential for function, requires the formation of oligomers with tetramers, pentamers, or hexamers observed depending on the species and experimental approach. We applied non-denaturing (native) mass spectrometry to five different homologs of MscL to determine the oligomeric state under more than 50 different experimental conditions elucidating lipid binding and subunit stoichiometry. We found equilibrium between pentameric and tetrameric species, which can be altered by detergent, disrupted by binding specific lipids, and perturbed by increasing temperature (37°C). We also established the presence of lipopolysaccharide bound to MscL and other membrane proteins expressed in Escherichia coli, revealing a potential source of heterogeneity. More generally, we highlight the use of mass spectrometry in probing membrane proteins under a variety of detergent-lipid environments relevant to structural biology.

  11. Chlorine isotope effects from isotope ratio mass spectrometry suggest intramolecular C-Cl bond competition in trichloroethene (TCE) reductive dehalogenation.

    Science.gov (United States)

    Cretnik, Stefan; Bernstein, Anat; Shouakar-Stash, Orfan; Löffler, Frank; Elsner, Martin

    2014-05-20

    Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms.

  12. Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE Reductive Dehalogenation

    Directory of Open Access Journals (Sweden)

    Stefan Cretnik

    2014-05-01

    Full Text Available Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (biochemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE dehalogenation was investigated. Selective biotransformation reactions (i of tetrachloroethene (PCE to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii of TCE to cis-1,2-dichloroethene (cis-DCE in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were −19.0‰ ± 0.9‰ (PCE and −12.2‰ ± 1.0‰ (TCE (95% confidence intervals. Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (−5.0‰ ± 0.1‰ and TCE (−3.6‰ ± 0.2‰. In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by −16.3‰ ± 1.4‰ (standard error than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of −2.4‰ ± 0.3‰ and the product chloride an isotope effect of −6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals. A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect. These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition. This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I or single electron transfer as reductive dehalogenation mechanisms.

  13. A history of mass spectrometry in Australia

    Energy Technology Data Exchange (ETDEWEB)

    Downard, K.M.; de Laeter, J.R. [University of Sydney, Sydney, NSW (Australia)

    2005-09-01

    An interest in mass spectrometry in Australia can be traced back to the 1920s with an early correspondence with Francis Aston who first visited these shores a decade earlier. The region has a rich tradition in both the development of the field and its application, from early measurements of ionization and appearance potentials by Jim Morrison at the Council for Scientific and Industrial Research (CSIR) around 1950 to the design and construction of instrumentation including the first use of a triple quadrupole mass spectrometer for tandem mass spectrometry, the first suite of programs to simulate ion optics (SIMION), the development of early TOF/TOF instruments and orthogonal acceleration and the local design and construction of several generations of a sensitive high-resolution ion microprobe (SHRIMP) instrument. Mass spectrometry has been exploited in the study and characterization of the constituents of this nation's unique flora and fauna from Australian apples, honey, tea plant and eucalyptus oil, snake, spider, fish and frog venoms, coal, oil, sediments and shale, environmental studies of groundwater to geochronological dating of limestone and granite, other terrestrial and meteoritic rocks and coral from the Great Barrier Reef. This article traces the history of mass spectrometry in its many guises and applications in the island continent of Australia. It focuses on contributions of scientists who played a major role in the early establishment of mass spectrometry in Australia. In general, those who are presently active in the field, and whose histories are incomplete, have been mentioned at best only briefly despite their important contributions to the field.

  14. Absorption mode FTICR mass spectrometry imaging.

    Science.gov (United States)

    Smith, Donald F; Kilgour, David P A; Konijnenburg, Marco; O'Connor, Peter B; Heeren, Ron M A

    2013-12-03

    Fourier transform ion cyclotron resonance mass spectrometry offers the highest mass resolving power for molecular imaging experiments. This high mass resolving power ensures that closely spaced peaks at the same nominal mass are resolved for proper image generation. Typically higher magnetic fields are used to increase mass resolving power. However, a gain in mass resolving power can also be realized by phase correction of the data for absorption mode display. In addition to mass resolving power, absorption mode offers higher mass accuracy and signal-to-noise ratio over the conventional magnitude mode. Here, we present the first use of absorption mode for Fourier transform ion cyclotron resonance mass spectrometry imaging. The Autophaser algorithm is used to phase correct each spectrum (pixel) in the image, and then, these parameters are used by the Chameleon work-flow based data processing software to generate absorption mode "Datacubes" for image and spectral viewing. Absorption mode reveals new mass and spatial features that are not resolved in magnitude mode and results in improved selected ion image contrast.

  15. Metabolite profiling of sucrose effect on the metabolism of Melissa officinalis by gas chromatography-mass spectrometry.

    Science.gov (United States)

    Kim, Sooah; Shin, Min Hye; Hossain, Md Aktar; Yun, Eun Ju; Lee, Hojoung; Kim, Kyoung Heon

    2011-04-01

    The effect of sugar on plant metabolism, which is known to be similar to hormone-like signaling, was metabolomically studied using Melissa officinalis (lemon balm). The metabolite profiles of M. officinalis treated with sucrose were analyzed by gas chromatography-mass spectrometry (GC-MS) and principal component analysis (PCA). A total of 64 metabolites from various chemical classes including alcohols, amines, amino acids, fatty acids, inorganic acids, organic acids, phosphates, and sugars were identified by GC-MS. Three groups treated with different sucrose concentrations were clearly separated by PCA of their metabolite profiles, indicating changes in the levels of many metabolites depending on the sucrose concentration. Metabolite profiling revealed that treatment with a higher sucrose level caused an increase in the levels of metabolites such as sugars, sugar alcohols, and sugar phosphates, which are related to the glycolytic pathway of M. officinalis. Furthermore, proline and succinic acid, which are associated with the proline-linked pentose phosphate pathway, the shikimic acid pathway, and the biosynthesis of phenylpropanoids, also increased with increasing sucrose concentration. Therefore, these metabolic changes induced by sucrose ultimately led to the increased production of flavonoids such as caffeic acid via the biosynthetic pathway of phenylpropanoids. This study demonstrated that the abundance changes in some primary and secondary metabolites were somewhat interlocked with each other in response to sucrose.

  16. The Effects of Added Hydrogen on Noble Gas Discharges Used as Ambient Desorption/Ionization Sources for Mass Spectrometry

    Science.gov (United States)

    Ellis, Wade C.; Lewis, Charlotte R.; Openshaw, Anna P.; Farnsworth, Paul B.

    2016-09-01

    We demonstrate the effectiveness of using hydrogen-doped argon as the support gas for the dielectric barrier discharge (DBD) ambient desorption/ionization (ADI) source in mass spectrometry. Also, we explore the chemistry responsible for the signal enhancement observed when using both hydrogen-doped argon and hydrogen-doped helium. The hydrogen-doped argon was tested for five analytes representing different classes of molecules. Addition of hydrogen to the argon plasma gas enhanced signals for gas-phase analytes and for analytes coated onto glass slides in positive and negative ion mode. The enhancements ranged from factors of 4 to 5 for gas-phase analytes and factors of 2 to 40 for coated slides. There was no significant increase in the background. The limit of detection for caffeine was lowered by a factor of 79 using H2/Ar and 2 using H2/He. Results are shown that help explain the fundamental differences between the pure-gas discharges and those that are hydrogen-doped for both argon and helium. Experiments with different discharge geometries and grounding schemes indicate that observed signal enhancements are strongly dependent on discharge configuration.

  17. The anti-atherosclerotic effect of tanshinol borneol ester using fecal metabolomics based on liquid chromatography-mass spectrometry.

    Science.gov (United States)

    Jia, Pu; Wang, Shixiang; Xiao, Chaoni; Yang, Lumeng; Chen, Yongyong; Jiang, Wei; Zheng, Xiaopu; Zhao, Guifang; Zang, Weijin; Zheng, Xiaohui

    2016-02-07

    Tanshinol borneol ester (DBZ) is a novel experimental compound that consists of two chemical structural units from danshensu and borneol. It exhibits efficacious anti-ischemic and anti-atherosclerosis activities in rats. A fecal metabolomics based on Liquid Chromatography-Mass Spectrometry combined with clinical histopathology and blood lipid estimation was employed to assess the efficacy and the metabolic changes caused by administration of DBZ in atherosclerotic rats. There were the typical pathological features of atherosclerosis and significantly increased levels of TC, TG and LDL-C in the atherosclerotic rat group. Nevertheless, atherosclerotic rats administered both DBZ (at a dose of 40 mg kg(-1)) and simvastatin (at a dose of 20 mg kg(-1)) showed good therapeutic effects. The results of the metabolomics studies showed that 55 differential metabolites such as sebacic acid, enterodiol, nonanedioic acid, dodecanedioic acid, cholic acid, 13(S)-HPODE, deoxycholic acid, some phosphatidylglycerol and phosphatidic acids were found, indicating that abnormal metabolism occurred in the pathways of fatty acid oxidation, linoleic acid metabolism, bile acid biosynthesis and glycerophospholipid metabolism in atherosclerotic rats. Compared to those in the model group, the contents of 41 differential metabolites showed a tendency to recover to a healthy level after DBZ administration. Metabolomics studies suggested that DBZ exhibited good treatment efficacy against atherosclerosis by adjusting disturbed metabolic pathways related to atherosclerosis. This study could provide an experimental basis for DBZ's application to act as a candidate drug with anti-atherosclerosis activity.

  18. A Comprehensive and Effective Mass Spectrometry-Based Screening Strategy for Discovery and Identification of New Brassinosteroids from Rice Tissues.

    Science.gov (United States)

    Xin, Peiyong; Yan, Jijun; Li, Bingbing; Fang, Shuang; Fan, Jinshi; Tian, Hailong; Shi, Yong; Tian, Weisheng; Yan, Cunyu; Chu, Jinfang

    2016-01-01

    The exploration and identification of new brassinosteroid (BR) compounds is critical to improve the biosynthetic research of BRs and expand the chemodiversity of active BRs. However, traditional methods are labor-intensive, time-consuming, and less sensitive. Here, we present a facile screening strategy for discovering and identifying novel BRs from plant tissues based on ultra-performance liquid chromatography-mass spectrometry (UPLC-MS). A total of 14 potential BRs were discovered from only 1 g of rice tissues and structurally elucidated by following a MS-based clue, acquired through multiple reaction monitoring (MRM) data-dependent enhanced product ion (EPI) scan, high resolution MS, and MS survey-dependent MS/MS. One of the 14 candidates was identified as 6-deoxo-28-homotyphasterol, a brand new BR compound that is reported for the first time in the BRs biosynthesis pathway. Detailed comparison with reference standards and quantitative level analysis in rice BR mutants confirmed the availability of the other candidates. This effective, yet simple method provides an efficient way to find more and more chemically new BR biosynthetic intermediates in plants, which is significant for complementing the biosynthesis and metabolism network of BRs. This strategy may also be used to discover unknown compounds of other plant hormone species as well as their key metabolites.

  19. Introduction to mass spectrometry-based proteomics

    DEFF Research Database (Denmark)

    Matthiesen, R.; Bunkenborg, J.

    2013-01-01

    for newcomers and give pointers to reference material. There are many applications of mass spectrometry in proteomics and each application is associated with some analytical choices, instrumental limitations and data processing steps that depend on the aim of the study and means of conducting it. Different...

  20. Atmospheric pressure femtosecond laser imaging mass spectrometry

    Science.gov (United States)

    Coello, Yves; Gunaratne, Tissa C.; Dantus, Marcos

    2009-02-01

    We present a novel imaging mass spectrometry technique that uses femtosecond laser pulses to directly ionize the sample. The method offers significant advantages over current techniques by eliminating the need of a laser-absorbing sample matrix, being suitable for atmospheric pressure sampling, and by providing 10μm resolution, as demonstrated here with a chemical image of vegetable cell walls.

  1. Nanostructure-initiator mass spectrometry biometrics

    Science.gov (United States)

    Leclerc, Marion; Bowen, Benjamin; Northen, Trent

    2015-09-08

    Several embodiments described herein are drawn to methods of identifying an analyte on a subject's skin, methods of generating a fingerprint, methods of determining a physiological change in a subject, methods of diagnosing health status of a subject, and assay systems for detecting an analyte and generating a fingerprint, by nanostructure-initiator mass spectrometry (NIMS).

  2. Nanostructure-initiator mass spectrometry biometrics

    Energy Technology Data Exchange (ETDEWEB)

    Leclerc, Marion; Bowen, Benjamin; Northen, Trent

    2015-09-08

    Several embodiments described herein are drawn to methods of identifying an analyte on a subject's skin, methods of generating a fingerprint, methods of determining a physiological change in a subject, methods of diagnosing health status of a subject, and assay systems for detecting an analyte and generating a fingerprint, by nanostructure-initiator mass spectrometry (NIMS).

  3. Mass spectrometry and bioinformatics analysis data

    Directory of Open Access Journals (Sweden)

    Mainak Dutta

    2015-03-01

    Full Text Available 2DE and 2D-DIGE based proteomics analysis of serum from women with endometriosis revealed several proteins to be dysregulated. A complete list of these proteins along with their mass spectrometry data and subsequent bioinformatics analysis are presented here. The data is related to “Investigation of serum proteome alterations in human endometriosis” by Dutta et al. [1].

  4. Introduction to mass spectrometry-based proteomics

    DEFF Research Database (Denmark)

    Matthiesen, R.; Bunkenborg, J.

    2013-01-01

    for newcomers and give pointers to reference material. There are many applications of mass spectrometry in proteomics and each application is associated with some analytical choices, instrumental limitations and data processing steps that depend on the aim of the study and means of conducting it. Different...

  5. Four decades of joy in mass spectrometry

    NARCIS (Netherlands)

    Nibbering, Nico M.M.

    2006-01-01

    Tremendous developments in mass spectrometry have taken place in the last 40 years. This holds for both the science and the instrumental revolutions in this field. In chemistry the research was heavily focused on organic molecules that upon electron ionization fragmented via complex mechanistic path

  6. Mass spectrometry in a multicusp ion source

    Energy Technology Data Exchange (ETDEWEB)

    Mullan, A.A. (Applied Physical Science, University of Ulster, Coleraine (Northern Ireland)); Graham, W.G. (Physics Department, Queen' s University, Belfast, (Northern Ireland))

    1990-08-05

    Mass spectrometry has been used for the detection of positive and negative ions in a multicusp ion source operating with both hydrogen and deuterium gas. The mass spectrometer operation has been optimized and it is shown that applying ion extraction voltages can disturb the discharge. Using this technique combined with a Langmuir probe technique we are able to study the positive ionic fractions present when operating with both gases (and the negative ion densities.)

  7. Polymer and Additive Mass Spectrometry Literature Review

    Energy Technology Data Exchange (ETDEWEB)

    Shear, Trevor Allan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-06-06

    The use of mass spectrometry in fields related to polymers has increased significantly over the past three decades and will be explored in this literature review. The importance of this technique is highlighted when exploring how polymers degrade, verifying purchased materials, and as internal requirements change. The primary focus will be on four ionization techniques and the triple quadrupole and quadrupole / time-of-flight mass spectrometers. The advantages and limitations of each will also be explored.

  8. Effect of D-allose on prostate cancer cell lines: phospholipid profiling by nanoflow liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Jeong, Rae Ung; Lim, Sangsoo; Kim, Myoung Ok; Moon, Myeong Hee

    2011-08-01

    D-Allose, a rare, naturally occurring monosaccharide, is known to exert anti-proliferative effects on cancer cells. The effects of D-allose on the cellular membranes of hormone-refractory prostate cancer cell line (DU145), hormone-sensitive prostate cancer cell line (LNCaP), and normal prostate epithelial cells (PrEC) were studied at the molecular level by phospholipid (PL) profiling using a shotgun lipidomic method. The molecular structures of 85 PL species including 23 phosphatidylcholines, 12 phosphatidylethanolamines (PEs), 11 phosphatidylserines (PSs), 16 phosphatidylinositols, 9 phosphatidic acids (PAs), and 14 phosphatidylglycerols (PGs) were identified by data-dependent collision-induced dissociation of nanoflow liquid chromatography-tandem mass spectrometry, and the PL amounts were quantified. The addition of D-allose to prostate cancer cell lines during their growth phases had negligible or decreased effects on the relative regulation of PL species, but several new PS molecules (two for DU145 and three for LNCaP) emerged. In contrast, experiments on the PrEC cell line revealed that some high abundant species (14:0/14:0-PE, 16:2/16:0-PG, and 20:6/18:1-PA) showed significant increases in concentration. These findings support a mechanism for the anti-proliferative effect of D-allose on prostate cancer cell lines that involves the induction of programmed cell death since PS molecules are known to induce apoptosis. Principal component analysis was carried out to examine differences in PL distributions among the three cell lines promoted by D-allose.

  9. Evaluation of matrix effect in isotope dilution mass spectrometry based on quantitative analysis of chloramphenicol residues in milk powder

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiu Qin; Yang, Zong; Zhang, Qing He, E-mail: qhzhang204@gmail.com; Li, Hong Mei

    2014-01-07

    Graphical abstract: -- Highlights: •We develop a strategy to evaluate matrix effect and its impact on the IDMS results. •Matrix effect and IDMS correction factor from different conditions are evaluated. •Ion suppression effect is observed in LLE and HLB pre-treated sample solutions. •Ion enhancement effect is found in MCX pre-treated sample solution. •IDMS correction factor in HLB and MCX solutions in three instruments is close to 1 -- Abstract: In the present study, we developed a comprehensive strategy to evaluate matrix effect (ME) and its impact on the results of isotope dilution mass spectrometry (IDMS) in analysis of chloramphenicol (CAP) residues in milk powder. Stable isotope-labeled internal standards do not always compensate ME, which brings the variation of the ratio (the peak area of analyte/the peak area of isotope). In our investigation, impact factors of this variation were studied in the extraction solution of milk powder using three mass spectrometers coupled with different ion source designs, and deuterium-labeled chloramphenicol (D5-CAP) was used as the internal standard. ME from mobile phases, sample solvents, pre-treatment methods, sample origins and instruments was evaluated, and its impact on the results of IDMS was assessed using the IDMS correction factor (θ). Our data showed that the impact of ME of mobile phase on the correction factor was significantly greater than that of sample solvent. Significant ion suppression and enhancement effects were observed in different pre-treated sample solutions. The IDMS correction factor in liquid–liquid extraction (LLE) and molecular imprinted polymer (MIP) extract with different instruments was greater or less 1.0, and the IDMS correction factor in hydrophilic lipophilic balance (HLB) and mix-mode cation exchange (MCX) extract with different instruments was all close to 1.0. To the instrument coupled with different ion source design, the impact of ME on IDMS quantitative results was

  10. Buffer salt effects in off-line coupling of capillary electrophoresis and mass spectrometry.

    Science.gov (United States)

    Marák, Jozef; Stanová, Andrea

    2014-05-01

    In this work, the impact of buffer salts/matrix effects on the signal in direct injection MS with an electrospray interface (DI-ESI-MS) following pITP fractionation of the sample was studied. A range of buffers frequently used in CE analyses (pH 3-10) was prepared containing 10, 50, and 90% v/v of ACN, respectively. The sets of calibration solutions of cetirizine (an antihistaminic drug with an amphiprotic character) within a 0.05-2.0 mg/L concentration range were prepared in different buffers. The greatest enhancements in the MS signal (in terms of change in the slope of the calibration line) were obtained for the beta-alanine buffer (pH 3.5) in positive ionization and for the borate buffer (pH 9.2) in negative ionization, respectively. The procedure was successfully applied to the analysis of buserelin (a peptidic drug). The slope of the calibration line for solutions containing the beta-alanine buffer with 50% of ACN was 4 times higher than for water or urine, respectively. This study clearly demonstrates that the buffer salt/matrix effects in an offline combination of pITP and DI-ESI-MS can also play a positive role, as they can enhance the signal in MS. A similar influence of the above effects can also be presumed in the CE techniques combined on-line with ESI-MS.

  11. Characterization of Membrane Protein-Lipid Interactions by Mass Spectrometry Ion Mobility Mass Spectrometry

    Science.gov (United States)

    Liu, Yang; Cong, Xiao; Liu, Wen; Laganowsky, Arthur

    2016-12-01

    Lipids in the biological membrane can modulate the structure and function of integral and peripheral membrane proteins. Distinguishing individual lipids that bind selectively to membrane protein complexes from an ensemble of lipid-bound species remains a daunting task. Recently, ion mobility mass spectrometry (IM-MS) has proven to be invaluable for interrogating the interactions between protein and individual lipids, where the complex undergoes collision induced unfolding followed by quantification of the unfolding pathway to assess the effect of these interactions. However, gas-phase unfolding experiments for membrane proteins are typically performed on the entire ensemble (apo and lipid bound species), raising uncertainty to the contribution of individual lipids and the species that are ejected in the unfolding process. Here, we describe the application of mass spectrometry ion mobility mass spectrometry (MS-IM-MS) for isolating ions corresponding to lipid-bound states of a model integral membrane protein, ammonia channel (AmtB) from Escherichia coli. Free of ensemble effects, MS-IM-MS reveals that bound lipids are ejected as neutral species; however, no correlation was found between the lipid-induced stabilization of complex and their equilibrium binding constants. In comparison to data obtained by IM-MS, there are surprisingly limited differences in stability measurements from IM-MS and MS-IM-MS. The approach described here to isolate ions of membrane protein complexes will be useful for other MS methods, such as surface induced dissociation or collision induced dissociation to determine the stoichiometry of hetero-oligomeric membrane protein complexes.

  12. Investigation of local primary structure effects on peroxynitrite-mediated tyrosine nitration using targeted mass spectrometry.

    Science.gov (United States)

    Seeley, Kent W; Stevens, Stanley M

    2012-03-16

    Protein-tyrosine nitration (PTN) is a posttranslational modification resulting from cellular nitrosative stress that has been implicated in a wide variety of disease states. Determination of factors that influence selectivity of PTN remains a major challenge due to several issues including low biological levels of PTN, proximity of target sites on a single analyte, and analytical limitations for site-specific quantification of the nitration modification. We report a systematic approach that addresses relevant contributing factors to PTN with particular focus on determining the effect of changing proximal amino acid side chain structure on tyrosine nitration yield. A trend was observed in which nitration yield tends to be greater when the tyrosine residue is surrounded by basic and/or uncharged polar residues compared to nitration levels observed when hydrophobic and acidic residues are proximal to the tyrosine residue. Moreover, an electric dipole effect was observed where a higher degree of charge asymmetry surrounding the tyrosine residue correlates with an increased tyrosine nitration yield in certain cases. The reported data are expected to facilitate site-specific prediction and validation of PTN, especially in cases of potential target residues that share a similar solvent exposure environment and contain elements of known higher-order structure. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Guideline on Isotope Dilution Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Gaffney, Amy [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2017-05-19

    Isotope dilution mass spectrometry is used to determine the concentration of an element of interest in a bulk sample. It is a destructive analysis technique that is applicable to a wide range of analytes and bulk sample types. With this method, a known amount of a rare isotope, or ‘spike’, of the element of interest is added to a known amount of sample. The element of interest is chemically purified from the bulk sample, the isotope ratio of the spiked sample is measured by mass spectrometry, and the concentration of the element of interest is calculated from this result. This method is widely used, although a mass spectrometer required for this analysis may be fairly expensive.

  14. Accelerator mass spectrometry: state of the art

    Energy Technology Data Exchange (ETDEWEB)

    Tuniz, C. [Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW (Australia)

    1996-12-31

    Accelerator Mass Spectrometry (AMS) is the analytical technique of choice for the detection of long-lived radionuclides which cannot be practically analysed with decay counting or conventional mass spectrometry. The main use of AMS has been in the analysis of radiocarbon and other cosmogenic radionuclides for archaeological, geological and environmental applications. In addition, AMS has been recently applied in biomedicine to study exposure of human tissues to chemicals and biomolecules at attomole levels. There is also a world-wide effort to analyse rare nuclides of heavier masses, such as long-lived actinides, with important applications in safeguards and nuclear waste disposal. The use of AMS is limited by the expensive accelerator technology required and there are several attempts to develop smaller and cheaper AMS spectrometers. 5 refs.

  15. Fluxomics: mass spectrometry versus quantitative imaging.

    Science.gov (United States)

    Wiechert, Wolfgang; Schweissgut, Oliver; Takanaga, Hitomi; Frommer, Wolf B

    2007-06-01

    The recent development of analytic high-throughput technologies enables us to take a bird's view of how metabolism is regulated in real time. We have known for a long time that metabolism is highly regulated at all levels, including transcriptional, posttranslational and allosteric controls. Flux through a metabolic or signaling pathway is determined by the activity of its individual components. Fluxomics aims to define the genes involved in regulation by following the flux. Two technologies are used to monitor fluxes. Pulse labeling of the organism or cell with a tracer, such as 13C, followed by mass spectrometric analysis of the partitioning of label into different compounds provides an efficient tool to study flux and to compare the effect of mutations on flux. The second approach is based on the use of flux sensors, proteins that respond with a conformational change to ligand binding. Fluorescence resonance energy transfer (FRET) detects the conformational change and serves as a proxy for ligand concentration. In contrast to the mass spectrometry assays, FRET nanosensors monitor only a single compound. Both methods provide high time resolution. The major advantages of FRET nanosensors are that they yield data with cellular and subcellular resolution and the method is minimally invasive.

  16. The effect of plasma operating parameters on analyte signals in inductively coupled plasma-mass spectrometry

    Science.gov (United States)

    Horlick, G.; Tan, S. H.; Vaughan, M. A.; Rose, C. A.

    Utilizing the SCIEX ICP-MS an extensive study of the effects that plasma operating parameters have on analyte ion signals in ICP-MS has been carried out. Parameters studied included aerosol flow rate (nebulizer pressure), auxiliary flow rate, power and sampling depth (sampling position from the load coil). The two key parameters are aerosol flow rate (nebulizer pressure) and power. Elements can be grouped into characteristic behaviour patterns based on the overall dependence of their ion count signal on these two parameters. The nebulizer pressure-power behavior patterns allow a sensible selection of compromise operating conditions and significantly clarify single parameter observations which often indicate confusing trends in behavior. In addition to characterizing analyte ion signals the parameter behavior plots have also been used to study oxide species and plus two ions in ICP-MS. While aerosol flow rate and power appear to be the key ICP parameters in ICP-MS, ion signals are dependent on sampling depth and auxiliary flow rate and some data are also presented illustrating the signal dependence on these two parameters.

  17. Microbial proteomics using mass spectrometry.

    Science.gov (United States)

    Hines, Harry B

    2012-01-01

    Proteomic analyses involve a series of intricate, interdependent steps involving approaches and technical issues that must be fully coordinated to obtain the optimal amount of required information about the test subject. Fortunately, many of these steps are common to most test subjects, requiring only modifications to or, in some cases, substitution of some of the steps to ensure they are relevant to the desired objective of a study. This fortunate occurrence creates an essential core of proteomic approaches and techniques that are consistently available for most studies, regardless of test subject. In this chapter, an overview of some of these core approaches, techniques, and mass spectrometric instrumentation is given, while indicating how such steps are useful for and applied to bacterial investigations. To exemplify how such proteomic concepts and techniques are applicable to bacterial investigations, a practical, quantitative method useful for bacterial proteomic analysis is presented with a discussion of possibilities, pitfalls, and some emerging technology to provide a compilation of information from the diverse literature that is intermingled with experimental experience.

  18. Space Applications of Mass Spectrometry. Chapter 31

    Science.gov (United States)

    Hoffman, John H.; Griffin, Timothy P.; Limero, Thomas; Arkin, C. Richard

    2010-01-01

    Mass spectrometers have been involved in essentially all aspects of space exploration. This chapter outlines some of these many uses. Mass spectrometers have not only helped to expand our knowledge and understanding of the world and solar system around us, they have helped to put man safely in space and expand our frontier. Mass spectrometry continues to prove to be a very reliable, robust, and flexible analytical instrument, ensuring that its use will continue to help aid our investigation of the universe and this small planet that we call home.

  19. Monitoring perinatal gut microbiota in mouse models by mass spectrometry approaches: parental genetic background and breastfeeding effects

    Directory of Open Access Journals (Sweden)

    Stefano Levi Mortera

    2016-09-01

    Full Text Available At birth, contact with external stimuli, such as nutrients derived from food, is necessary to modulate the symbiotic balance between commensal and pathogenic bacteria, protect against bacterial dysbiosis, and initiate the development of the mucosal immune response. Among a variety of different feeding patterns, breastfeeding represents the best modality. In fact, the capacity of breast milk to modulate the composition of infants’ gut microbiota leads to beneficial effects on their health. In this study, we used newborn mice as a model to evaluate the effect of parental genetic background (i.e., IgA-producing mice and IgA-deficient mice and feeding modulation (i.e., maternal feeding and cross-feeding on the onset and shaping of gut microbiota after birth. To investigate these topics, we used either a culturomic approach that employed Matrix Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometry (MS, or bottom-up Liquid Chromatography, with subsequent MSMS shotgun metaproteomic analysis that compared and assembled results of the two techniques. We found that the microbial community was enriched by lactic acid bacteria when pups were breastfed by wild-type (WT mothers, while IgA-deficient milk led to an increase in the opportunistic bacterial pathogen (OBP population. Cross-feeding results suggested that IgA supplementation promoted the exclusion of some OBPs and the temporary appearance of beneficial species in pups fed by WT foster mothers. Our results show that both techniques yield a picture of microbiota from different angles and with varying depths. In particular, our metaproteomic pipeline was found to be a reliable tool in the description of microbiota. Data from these studies are available via ProteomeXchange, with identifier PXD004033.

  20. Monitoring Perinatal Gut Microbiota in Mouse Models by Mass Spectrometry Approaches: Parental Genetic Background and Breastfeeding Effects

    Science.gov (United States)

    Levi Mortera, Stefano; Del Chierico, Federica; Vernocchi, Pamela; Rosado, Maria M.; Cavola, Agnese; Chierici, Marco; Pieroni, Luisa; Urbani, Andrea; Carsetti, Rita; Lante, Isabella; Dallapiccola, Bruno; Putignani, Lorenza

    2016-01-01

    At birth, contact with external stimuli, such as nutrients derived from food, is necessary to modulate the symbiotic balance between commensal and pathogenic bacteria, protect against bacterial dysbiosis, and initiate the development of the mucosal immune response. Among a variety of different feeding patterns, breastfeeding represents the best modality. In fact, the capacity of breast milk to modulate the composition of infants’ gut microbiota leads to beneficial effects on their health. In this study, we used newborn mice as a model to evaluate the effect of parental genetic background (i.e., IgA-producing mice and IgA-deficient mice) and feeding modulation (i.e., maternal feeding and cross-feeding) on the onset and shaping of gut microbiota after birth. To investigate these topics, we used either a culturomic approach that employed Matrix Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometry (MS), or bottom–up Liquid Chromatography, with subsequent MSMS shotgun metaproteomic analysis that compared and assembled results of the two techniques. We found that the microbial community was enriched by lactic acid bacteria when pups were breastfed by wild-type (WT) mothers, while IgA-deficient milk led to an increase in the opportunistic bacterial pathogen (OBP) population. Cross-feeding results suggested that IgA supplementation promoted the exclusion of some OBPs and the temporary appearance of beneficial species in pups fed by WT foster mothers. Our results show that both techniques yield a picture of microbiota from different angles and with varying depths. In particular, our metaproteomic pipeline was found to be a reliable tool in the description of microbiota. Data from these studies are available via ProteomeXchange, with identifier PXD004033. PMID:27725814

  1. Direct analysis of samples by mass spectrometry: From elements to bio-molecules using laser ablation inductively couple plasma mass spectrometry and laser desorption/ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Perdian, David C. [Iowa State Univ., Ames, IA (United States)

    2009-01-01

    Mass spectrometric methods that are able to analyze solid samples or biological materials with little or no sample preparation are invaluable to science as well as society. Fundamental research that has discovered experimental and instrumental parameters that inhibit fractionation effects that occur during the quantification of elemental species in solid samples by laser ablation inductively coupled plasma mass spectrometry is described. Research that determines the effectiveness of novel laser desorption/ionization mass spectrometric methods for the molecular analysis of biological tissues at atmospheric pressure and at high spatial resolution is also described. A spatial resolution is achieved that is able to analyze samples at the single cell level.

  2. Use of mass spectrometry to study signaling pathways

    DEFF Research Database (Denmark)

    Pandey, A; Andersen, Jens S.; Mann, M

    2000-01-01

    biochemical assays have been used to identify molecules involved in signaling pathways. Lately, mass spectrometry, combined with elegant biochemical approaches, has become a powerful tool for identifying proteins and posttranslational modifications. With this protocol, we hope to bridge the gap between...... identification by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry and nanoelectrospray tandem mass spectrometry. We discuss the special requirements for the identification of phosphorylation sites in proteins by mass spectrometry. We describe enrichment of phosphopeptides from unseparated...

  3. Effective Application of Bicelles for Conformational Analysis of G Protein-Coupled Receptors by Hydrogen/Deuterium Exchange Mass Spectrometry

    Science.gov (United States)

    Duc, Nguyen Minh; Du, Yang; Thorsen, Thor S.; Lee, Su Youn; Zhang, Cheng; Kato, Hideaki; Kobilka, Brian K.; Chung, Ka Young

    2015-05-01

    G protein-coupled receptors (GPCRs) have important roles in physiology and pathology, and 40% of drugs currently on the market target GPCRs for the treatment of various diseases. Because of their therapeutic importance, the structural mechanism of GPCR signaling is of great interest in the field of drug discovery. Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is a useful tool for analyzing ligand binding sites, the protein-protein interaction interface, and conformational changes of proteins. However, its application to GPCRs has been limited for various reasons, including the hydrophobic nature of GPCRs and the use of detergents in their preparation. In the present study, we tested the application of bicelles as a means of solubilizing GPCRs for HDX-MS studies. GPCRs (e.g., β2-adrenergic receptor [β2AR], μ-opioid receptor, and protease-activated receptor 1) solubilized in bicelles produced better sequence coverage (greater than 90%) than GPCRs solubilized in n-dodecyl-β-D-maltopyranoside (DDM), suggesting that bicelles are a more effective method of solubilization for HDX-MS studies. The HDX-MS profile of β2AR in bicelles showed that transmembrane domains (TMs) undergo lower deuterium uptake than intracellular or extracellular regions, which is consistent with the fact that the TMs are highly ordered and embedded in bicelles. The overall HDX-MS profiles of β2AR solubilized in bicelles and in DDM were similar except for intracellular loop 3. Interestingly, we detected EX1 kinetics, an important phenomenon in protein dynamics, at the C-terminus of TM6 in β2AR. In conclusion, we suggest the application of bicelles as a useful method for solubilizing GPCRs for conformational analysis by HDX-MS.

  4. Systematic Temperature Effects in the Argon Cluster Ion Sputter Depth Profiling of Organic Materials Using Secondary Ion Mass Spectrometry

    Science.gov (United States)

    Seah, Martin P.; Havelund, Rasmus; Gilmore, Ian S.

    2016-08-01

    A study is presented of the effects of sample temperature on the sputter depth profiling of two organic materials, NPB ( N,N'-Di(1-naphthyl)- N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) and Irganox 1010, using a 5 keV Ar2000 + cluster ion beam and analysis by secondary ion mass spectrometry. It is shown that at low temperatures, the yields increase slowly with temperature in accordance with the Universal Sputtering Yield equation where the energy term is now modified by Trouton's rule. This occurs up to a transition temperature, T T, which is, in turn, approximately 0.8 T M, where T M is the sample melting temperature in Kelvin. For NPB and Irganox 1010, these transition temperatures are close to 15 °C and 0 °C, respectively. Above this temperature, the rate of increase of the sputtering yield rises by an order of magnitude. During sputtering, the depth resolution also changes with temperature with a very small change occurring below T T. At higher temperatures, the depth resolution improves but then rapidly degrades, possibly as a result first of local crater surface diffusion and then of bulk inter-diffusion. The secondary ion spectra also change with temperature with the intensities of the molecular entities increasing least. This agrees with a model in which the molecular entities arise near the crater rim. It is recommended that for consistent results, measurements for organic materials are always made at temperatures significantly below T T or 0.8 T M, and this is generally below room temperature.

  5. Boundaries of mass resolution in native mass spectrometry

    NARCIS (Netherlands)

    Lössl, Philip; Snijder, Joost; Heck, Albert J R

    2014-01-01

    Over the last two decades, native mass spectrometry (MS) has emerged as a valuable tool to study intact proteins and noncovalent protein complexes. Studied experimental systems range from small-molecule (drug)-protein interactions, to nanomachineries such as the proteasome and ribosome, to even viru

  6. Crux: rapid open source protein tandem mass spectrometry analysis.

    Science.gov (United States)

    McIlwain, Sean; Tamura, Kaipo; Kertesz-Farkas, Attila; Grant, Charles E; Diament, Benjamin; Frewen, Barbara; Howbert, J Jeffry; Hoopmann, Michael R; Käll, Lukas; Eng, Jimmy K; MacCoss, Michael J; Noble, William Stafford

    2014-10-03

    Efficiently and accurately analyzing big protein tandem mass spectrometry data sets requires robust software that incorporates state-of-the-art computational, machine learning, and statistical methods. The Crux mass spectrometry analysis software toolkit ( http://cruxtoolkit.sourceforge.net ) is an open source project that aims to provide users with a cross-platform suite of analysis tools for interpreting protein mass spectrometry data.

  7. Preliminary Investigation into Pyrotechnic Chemical Products via Mass Spectrometry Techniques

    Science.gov (United States)

    2015-03-11

    via Mass Spectrometry Techniques 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Jonathan Dilger, Eric...undesirable side reactions within the combustion. Mass spectrometry (MS) enables the rapid analysis of these products with instrumentation that offers...predicted by theory. 15. SUBJECT TERMS mass spectrometry , gas chromatography, pyrolysis, combustion products, pyrotechnics 16. SECURITY CLASSIFICATION OF

  8. Application of Nanodiamonds in Biomolecular Mass Spectrometry

    OpenAIRE

    Ping Cheng; Xianglei Kong

    2010-01-01

    The combination of nanodiamond (ND) with biomolecular mass spectrometry (MS) makes rapid, sensitive detection of biopolymers from complex biosamples feasible. Due to its chemical inertness, optical transparency and biocompatibility, the advantage of NDs in MS study is unique. Furthermore, functionalization on the surfaces of NDs expands their application in the fields of proteomics and genomics for specific requirements greatly. This review presents methods of MS analysis based on solid phase...

  9. Laser mass spectrometry for selective ultratrace determination

    CERN Document Server

    Wendt, K; Müller, P; Nörtershäuser, W; Schmitt, A; Trautmann, N; Bushaw, B A

    1999-01-01

    Resonance ionization mass spectrometry has been explored in respect to its capabilities for isobaric suppression, isotopic selectivity, and overall efficiency. Theoretical calculations within the density matrix formalism on coherent multi-step excitation processes predict high specifications, which have been confirmed by spectroscopic measurements in Ca and which make the technique attractive for ultratrace detection. Analytical applications are found in the determination of the ultratrace isotope sup 4 sup 1 Ca for cosmochemical, radiodating, and medical applications.

  10. Monolithic multinozzle emitters for nanoelectrospray mass spectrometry

    Science.gov (United States)

    Wang, Daojing; Yang, Peidong; Kim, Woong; Fan, Rong

    2011-09-20

    Novel and significantly simplified procedures for fabrication of fully integrated nanoelectrospray emitters have been described. For nanofabricated monolithic multinozzle emitters (NM.sup.2 emitters), a bottom up approach using silicon nanowires on a silicon sliver is used. For microfabricated monolithic multinozzle emitters (M.sup.3 emitters), a top down approach using MEMS techniques on silicon wafers is used. The emitters have performance comparable to that of commercially-available silica capillary emitters for nanoelectrospray mass spectrometry.

  11. Effect of surface-enhanced laser desorption/ionization time-of-flight mass spectrometry on identifing biomarkers of endometriosis

    Institute of Scientific and Technical Information of China (English)

    ZHANG Hong; FENG Jie; CHANG Xiao-hong; LI Zhong-xing; WU Xiao-yi; CUI Heng

    2009-01-01

    Background Endometriosis is a common gynecological disease. This study aimed to screen proteins that were expressed differently in patients with endometriosis versus normal controls using proteomic techniques, surface-enhanced laser desorption/ionization time-of-flight mass spectrometry (SELDI-TOF-MS).Methods Protein chip SELDI-TOF-MS combines the advantages of microarray and mass spectrometry, and can screen latent markers in sera of patients with endometriosis. Serum samples from patients and normal volunteers were analyzed by SELDI-TOF-MS.Results After comparing the serum protein spectra of 36 patients with 24 normal controls, 24 differently expressed potential biomarkers (P <0.01) were identified. Using Biomarker Pattern software, we established a tree model of the 60 serum protein spectra. When using the three biomarkers to classify the samples, the sensitivity for diagnosing endometriosis was 91.7%, specificity was 95.8%, and coincidence rate was 93.3%. Then we used serum samples from 12 patients and 8 normal controls to validate the tree model and report the sensitivity for diagnosing endometriosis was 91.7%, specificity was 75%, and coincidence rate was 85%.Conclusions SELDI-TOF-MS may be a useful tool in high-risk population screening for endometriosis. The identification and application of the biomarkers need to further study.

  12. Trends in mass spectrometry instrumentation for proteomics.

    Science.gov (United States)

    Smith, Richard D

    2002-12-01

    Mass spectrometry has become a primary tool for proteomics because of its capabilities for rapid and sensitive protein identification and quantitation. It is now possible to identify thousands of proteins from microgram sample quantities in a single day and to quantify relative protein abundances. However, the need for increased capabilities for proteome measurements is immense and is now driving both new strategies and instrument advances. These developments include those based on integration with multi-dimensional liquid separations and high accuracy mass measurements and promise more than order of magnitude improvements in sensitivity, dynamic range and throughput for proteomic analyses in the near future.

  13. Effects of Solvent and Ion Source Pressure on the Analysis of Anabolic Steroids by Low Pressure Photoionization Mass Spectrometry

    Science.gov (United States)

    Liu, Chengyuan; Zhu, Yanan; Yang, Jiuzhong; Zhao, Wan; Lu, Deen; Pan, Yang

    2017-01-01

    Solvent and ion source pressure were two important factors relating to the photon induced ion-molecule reactions in low pressure photoionization (LPPI). In this work, four anabolic steroids were analyzed by LPPI mass spectrometry. Both the ion species present and their relative abundances could be controlled by switching the solvent and adjusting the ion source pressure. Whereas M•+, MH+, [M - H2O]+, and solvent adducts were observed in positive LPPI, [M - H]- and various oxidation products were abundant in negative LPPI. Changing the solvent greatly affected formation of the ion species in both positive and negative ion modes. The ion intensities of the solvent adduct and oxygen adduct were selectively enhanced when the ion source pressure was elevated from 68 to 800 Pa. The limit of detection could be decreased by increasing the ion source pressure.

  14. Accelerator Mass Spectrometry (AMS) 1977-1987

    Science.gov (United States)

    Gove, H. E.; Purser, K. H.; Litherland, A. E.

    2010-04-01

    The eleventh Accelerator Mass Spectrometry (AMS 11) Conference took place in September 2008, the Thirtieth Anniversary of the first Conference. That occurred in 1978 after discoveries with nuclear physics accelerators in 1977. Since the first Conference there have now been ten further conferences on the development and applications of what has become known as AMS. This is the accepted acronym for the use of accelerators, together with nuclear and atomic physics techniques, to enhance the performance of mass spectrometers for the detection and measurement of rare long-lived radioactive elements such as radiocarbon. This paper gives an outline of the events that led to the first conference together with a brief account of the first four conferences before the introduction of the second generation of accelerator mass spectrometers at AMS 5.

  15. Dissecting the effect of RNA aptamer binding on the dynamics of plasminogen activator inhibitor 1 using hydrogen/deuterium exchange mass spectrometry

    DEFF Research Database (Denmark)

    Trelle, Morten B; Dupont, Daniel Miotto; Madsen, Jeppe Buur

    2014-01-01

    , about their effects on protein conformation and dynamics. We have employed hydrogen/deuterium exchange (HDX) mass spectrometry to study the effect of RNA aptamers on the structural flexibility of the serpin plasminogen activator inhibitor-1 (PAI-1). The aptamers have characteristic effects...... of the aptamers to PAI-1 is associated with substantial and widespread protection against deuterium uptake in PAI-1. The aptamers induce protection against exchange with the solvent both in the protein-aptamer interface as well as in other specific areas. Interestingly, the aptamers induce substantial protection...

  16. Simultaneous mass detection for direct inlet mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, R.L.

    1979-05-01

    The evolution of analytical techniques for application in trace analysis has led to interest in practical methods for real-time monitoring. Direct inlet mass spectrometry (DIMS) has been the subject of considerable activity in recent years. A DIMS instrument is described which consists of an inlet system designed to permit particles entrained in the inlet air stream to strike a hot, oxidized rhenium filament which serves as a surface ionization source. A mass analyzer and detection system then permits identification of the elemental composition of particulates which strike the filament.

  17. Characterization of Wax Esters by Electrospray Ionization Tandem Mass Spectrometry: Double Bond Effect and Unusual Product Ions.

    Science.gov (United States)

    Chen, Jianzhong; Green, Kari B; Nichols, Kelly K

    2015-08-01

    A series of different types of wax esters (represented by RCOOR') were systematically studied by using electrospray ionization (ESI) collision-induced dissociation tandem mass spectrometry (MS/MS) along with pseudo MS(3) (in-source dissociation combined with MS/MS) on a quadrupole time-of-flight (Q-TOF) mass spectrometer. The tandem mass spectra patterns resulting from dissociation of ammonium/proton adducts of these wax esters were influenced by the wax ester type and the collision energy applied. The product ions [RCOOH2](+), [RCO](+) and [RCO-H2O](+) that have been reported previously were detected; however, different primary product ions were demonstrated for the three wax ester types including: (1) [RCOOH2](+) for saturated wax esters, (2) [RCOOH2](+), [RCO](+) and [RCO-H2O](+) for unsaturated wax esters containing only one double bond in the fatty acid moiety or with one additional double bond in the fatty alcohol moiety, and (3) [RCOOH2](+) and [RCO](+) for unsaturated wax esters containing a double bond in the fatty alcohol moiety alone. Other fragments included [R'](+) and several series of product ions for all types of wax esters. Interestingly, unusual product ions were detected, such as neutral molecule (including water, methanol and ammonia) adducts of [RCOOH2](+) ions for all types of wax esters and [R'-2H](+) ions for unsaturated fatty acyl-containing wax esters. The patterns of tandem mass spectra for different types of wax esters will inform future identification and quantification approaches of wax esters in biological samples as supported by a preliminary study of quantification of isomeric wax esters in human meibomian gland secretions.

  18. Mass spectrometry imaging: applications to food science.

    Science.gov (United States)

    Taira, Shu; Uematsu, Kohei; Kaneko, Daisaku; Katano, Hajime

    2014-01-01

    Two-dimensional mass spectrometry (MS) analysis of biological samples by means of what is called MS imaging (MSI) is now being used to analyze analyte distribution because it facilitates determination of the existence (what is it?) and localization (where is it?) of biomolecules. Reconstruction of mass image by target signal is given after two-dimensional MS measurements on a sample section. From only one section, we can understand the existence and localization of many molecules without the need of an antibody or fluorescent reagent. In this review, we introduce the analysis of localization of functional constituents and nutrients in herbal medicine products via MSI. The ginsenosides were mainly distributed in the periderm and the tip region of the root of Panax ginseng. The capsaicin was found to be more dominantly localized in the placenta than the pericarp and seed in Capsicum fruits. We expect MSI will be a useful technique for optical quality assurance.

  19. Radiocarbon positive-ion mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Freeman, Stewart P.H.T.; Shanks, Richard P. [Scottish Universities Environmental Research Centre (SUERC), Scottish Enterprise Technology Park, East Kilbride G75 0QF (United Kingdom); Donzel, Xavier; Gaubert, Gabriel [Pantechnik S.A., 13 Rue de la Résistance, 14400 Bayeux (France)

    2015-10-15

    Proof-of-principle of a new mass spectrometric technique for radiocarbon measurement is demonstrated. Interfering nitrogen and hydrocarbon molecules are largely eliminated in a charge-exchange cell operating on non-metallic gas. The positive-to-negative ion conversion is the reverse of that conventionally used in accelerator mass spectrometry (AMS) and is compatible with plasma ion sources that may be significantly more efficient and capable of greater output than are AMS sputter ion sources. The Nanogan electron cyclotron resonance (ECR) ion source employed exhibited no sample memory and the >50 kyrs age range of AMS was reproduced. A bespoke prototype new instrument is now required to optimise the plasma and cell physics and to realise hypothetical performance gains over AMS.

  20. Proteome analysis of adenovirus using mass spectrometry.

    Science.gov (United States)

    Lind, Sara Bergström; Artemenko, Konstantin A; Pettersson, Ulf

    2014-01-01

    Analysis of proteins and their posttranslational modifications is important for understanding different biological events. For analysis of viral proteomes, an optimal protocol includes production of a highly purified virus that can be investigated with a high-resolving analytical method. In this Methods in Molecular Biology paper we describe a working strategy for how structural proteins in the Adenovirus particle can be studied using liquid chromatography-high-resolving mass spectrometry. This method provides information on the chemical composition of the virus particle. Further, knowledge about amino acids carrying modifications that could be essential for any part of the virus life cycle is collected. We describe in detail alternatives available for preparation of virus for proteome analysis as well as choice of mass spectrometric instrumentation suitable for this kind of analysis.

  1. Mass Spectrometry for Rapid Characterization of Microorganisms

    Science.gov (United States)

    Demirev, Plamen A.; Fenselau, Catherine

    2008-07-01

    Advances in instrumentation, proteomics, and bioinformatics have contributed to the successful applications of mass spectrometry (MS) for detection, identification, and classification of microorganisms. These MS applications are based on the detection of organism-specific biomarker molecules, which allow differentiation between organisms to be made. Intact proteins, their proteolytic peptides, and nonribosomal peptides have been successfully utilized as biomarkers. Sequence-specific fragments for biomarkers are generated by tandem MS of intact proteins or proteolytic peptides, obtained after, for instance, microwave-assisted acid hydrolysis. In combination with proteome database searching, individual biomarker proteins are unambiguously identified from their tandem mass spectra, and from there the source microorganism is also identified. Such top-down or bottom-up proteomics approaches permit rapid, sensitive, and confident characterization of individual microorganisms in mixtures and are reviewed here. Examples of MS-based functional assays for detection of targeted microorganisms, e.g., Bacillus anthracis, in environmental or clinically relevant backgrounds are also reviewed.

  2. Imaging mass spectrometry at cellular length scales.

    Science.gov (United States)

    Altelaar, A F Maarten; Luxembourg, Stefan L; McDonnell, Liam A; Piersma, Sander R; Heeren, Ron M A

    2007-01-01

    Imaging mass spectrometry (IMS) allows the direct investigation of both the identity and the spatial distribution of the molecular content directly in tissue sections, single cells and many other biological surfaces. In this protocol, we present the steps required to retrieve the molecular information from tissue sections using matrix-enhanced (ME) and metal-assisted (MetA) secondary ion mass spectrometry (SIMS) as well as matrix-assisted laser desorption/ionization (MALDI) IMS. These techniques require specific sample preparation steps directed at optimal signal intensity with minimal redistribution or modification of the sample analytes. After careful sample preparation, different IMS methods offer a unique discovery tool in, for example, the investigation of (i) drug transport and uptake, (ii) biological processing steps and (iii) biomarker distributions. To extract the relevant information from the huge datasets produced by IMS, new bioinformatics approaches have been developed. The duration of the protocol is highly dependent on sample size and technique used, but on average takes approximately 5 h.

  3. Mass Spectrometry on Future Mars Landers

    Science.gov (United States)

    Brinckerhoff, W. B.; Mahaffy, P. R.

    2011-01-01

    Mass spectrometry investigations on the 2011 Mars Science Laboratory (MSL) and the 2018 ExoMars missions will address core science objectives related to the potential habitability of their landing site environments and more generally the near-surface organic inventory of Mars. The analysis of complex solid samples by mass spectrometry is a well-known approach that can provide a broad and sensitive survey of organic and inorganic compounds as well as supportive data for mineralogical analysis. The science value of such compositional information is maximized when one appreciates the particular opportunities and limitations of in situ analysis with resource-constrained instrumentation in the context of a complete science payload and applied to materials found in a particular environment. The Sample Analysis at Mars (SAM) investigation on MSL and the Mars Organic Molecule Analyzer (MOMA) investigation on ExoMars will thus benefit from and inform broad-based analog field site work linked to the Mars environments where such analysis will occur.

  4. Accurate Mass Determination of Amino Alcohols by Turboionspray/Time-of-Flight Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    GENG,Yu(耿昱); GUO,Yin-Long(郭寅龙); ZHAO,Shi-Min(赵士民); MA,Sheng-Ming(麻生明)

    2002-01-01

    Amino alcohols were studied by turboionspray/time-of-flight mass spectrometry (TIS/TOF-MS) with the aim of determining the accurate mass of their protonated molecule ions.Polyethylene glycol (PEG) was used as the internal reference.Compared with the theoretical values, all relative errors were less than 5×10-6. The effects of nozzle potential, nozzle temperature, acquisition rate etc. on accurate mass determination were also studied.

  5. Isotope ratio analysis by Orbitrap mass spectrometry

    Science.gov (United States)

    Eiler, J. M.; Chimiak, L. M.; Dallas, B.; Griep-Raming, J.; Juchelka, D.; Makarov, A.; Schwieters, J. B.

    2016-12-01

    Several technologies are being developed to examine the intramolecular isotopic structures of molecules (i.e., site-specific and multiple substitution), but various limitations in sample size and type or (for IRMS) resolution have so far prevented the creation of a truly general technique. We will discuss the initial findings of a technique based on Fourier transform mass spectrometry, using the Thermo Scientific Q Exactive GC — an instrument that contains an Orbitrap mass analyzer. Fourier transform mass spectrometry is marked by exceptionally high mass resolutions (the Orbitrap reaches M/∆M in the range 250,000-1M in the mass range of greatest interest, 50-200 amu). This allows for resolution of a large range of nearly isobaric interferences for isotopologues of volatile and semi-volatile compounds (i.e., involving isotopes of H, C, N, O and S). It also provides potential to solve very challenging mass resolution problems for isotopic analysis of other, heavier elements. Both internal and external experimental reproducibilities of isotope ratio analyses using the Orbitrap typically conform to shot-noise limits down to levels of 0.2 ‰ (1SE), and routinely in the range 0.5-1.0 ‰, with similar accuracy when standardized to concurrently run reference materials. Such measurements can be made without modifications to the ion optics of the Q Exactive GC, but do require specially designed sample introduction devices to permit sample/standard comparison and long integration times. The sensitivity of the Q Exactive GC permits analysis of sub-nanomolar samples and quantification of multiply-substituted species. The site-specific capability of this instrument arises from the fact that mass spectra of molecular analytes commonly contain diverse fragment ion species, each of which samples a specific sub-set of molecular sites. We will present applications of this technique to the biological and abiological chemistry of amino acids, forensic identification of

  6. Probing of the combined effect of bisquaternary ammonium antimicrobial agents and acetylsalicylic acid on model phospholipid membranes: differential scanning calorimetry and mass spectrometry studies.

    Science.gov (United States)

    Kasian, N A; Pashynska, V A; Vashchenko, O V; Krasnikova, A O; Gömöry, A; Kosevich, M V; Lisetski, L N

    2014-12-01

    A model molecular biosystem of hydrated dipalmitoylphosphatidylcholine (DPPC) bilayers that mimics cell biomembranes is used to probe combined membranotropic effects of drugs by instrumental techniques of molecular biophysics. Differential scanning calorimetry reveals that doping of the DPPC model membrane with individual bisquaternary ammonium compounds (BQAC) decamethoxinum, ethonium, thionium and acetylsalicylic acid (ASA) leads to lowering of the membrane melting temperature (Tm) pointing to membrane fluidization. Combined application of the basic BQAC and acidic ASA causes an opposite effect on Tm (increase), corresponding to the membrane densification. Thus, modulation of the membranotropic effects upon combined use of the drugs studied can be revealed at the level of model membranes. Formation of noncovalent supramolecular complexes of the individual BQACs and ASA with DPPC molecules, which may be involved in the mechanism of the drug-membrane interaction at the molecular level, is demonstrated by electrospray ionization (ESI) mass spectrometry. In the ternary (DPPC + ASA + BQAC) model systems, the stable complexes of the BQAC dication with the ASA anion, which may be responsible for modulation of the membranotropic effects of the drugs, were recorded by ESI mass spectrometry. The proposed approach can be further developed for preliminary evaluation of the combined effects of the drugs at the level of model lipid membranes prior to tests on living organisms.

  7. Ambient ionization mass spectrometry: A tutorial

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Min-Zong; Cheng, Sy-Chi; Cho, Yi-Tzu [Department of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan (China); Shiea, Jentaie, E-mail: jetea@fac.nsysu.edu.tw [Department of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan (China); Cancer Center, Kaohsiung Medical University, Kaohsiung, Taiwan (China)

    2011-09-19

    Highlights: {yields} Ambient ionization technique allows the direct analysis of sample surfaces with little or no sample pretreatment. {yields} We sort ambient ionization techniques into three main analytical strategies, direct ionization, direct desorption/ionization, and two-step ionization. {yields} The underlying principles of operation, ionization processes, detecting mass ranges, sensitivity, and representative applications of these techniques are described and compared. - Abstract: Ambient ionization is a set of mass spectrometric ionization techniques performed under ambient conditions that allows the direct analysis of sample surfaces with little or no sample pretreatment. Using combinations of different types of sample introduction systems and ionization methods, several novel techniques have been developed over the last few years with many applications (e.g., food safety screening; detection of pharmaceuticals and drug abuse; monitoring of environmental pollutants; detection of explosives for antiterrorism and forensics; characterization of biological compounds for proteomics and metabolomics; molecular imaging analysis; and monitoring chemical and biochemical reactions). Electrospray ionization and atmospheric pressure chemical ionization are the two main ionization principles most commonly used in ambient ionization mass spectrometry. This tutorial paper provides a review of the publications related to ambient ionization techniques. We describe and compare the underlying principles of operation, ionization processes, detecting mass ranges, sensitivity, and representative applications of these techniques.

  8. Multinozzle Emitter Arrays for Nanoelectrospray Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Mao, Pan; Wang, Hung-Ta; Yang, Peidong; Wang, Daojing

    2011-06-16

    Mass spectrometry (MS) is the enabling technology for proteomics and metabolomics. However, dramatic improvements in both sensitivity and throughput are still required to achieve routine MS-based single cell proteomics and metabolomics. Here, we report the silicon-based monolithic multinozzle emitter array (MEA), and demonstrate its proof-of-principle applications in high-sensitivity and high-throughput nanoelectrospray mass spectrometry. Our MEA consists of 96 identical 10-nozzle emitters in a circular array on a 3-inch silicon chip. The geometry and configuration of the emitters, the dimension and number of the nozzles, and the micropillar arrays embedded in the main channel, can be systematically and precisely controlled during the microfabrication process. Combining electrostatic simulation and experimental testing, we demonstrated that sharpened-end geometry at the stem of the individual multinozzle emitter significantly enhanced the electric fields at its protruding nozzle tips, enabling sequential nanoelectrospray for the high-density emitter array. We showed that electrospray current of the multinozzle emitter at a given total flow rate was approximately proportional to the square root of the number of its spraying-nozzles, suggesting the capability of high MS sensitivity for multinozzle emitters. Using a conventional Z-spray mass spectrometer, we demonstrated reproducible MS detection of peptides and proteins for serial MEA emitters, achieving sensitivity and stability comparable to the commercial capillary emitters. Our robust silicon-based MEA chip opens up the possibility of a fully-integrated microfluidic system for ultrahigh-sensitivity and ultrahigh-throughput proteomics and metabolomics.

  9. Mass spectrometry for high-throughput metabolomics analysis of urine

    OpenAIRE

    Abdelrazig, Salah M.A.

    2015-01-01

    Direct electrospray ionisation-mass spectrometry (direct ESI-MS), by omitting the chromatographic step, has great potential for application as a high-throughput approach for untargeted urine metabolomics analysis compared to liquid chromatography-mass spectrometry (LC-MS). The rapid development and technical innovations revealed in the field of ambient ionisation MS such as nanoelectrospray ionisation (nanoESI) chip-based infusion and liquid extraction surface analysis mass spectrometry (LESA...

  10. High-resolution laser ablation-inductively coupled plasma-mass spectrometry imaging of cisplatin-induced nephrotoxic side effects.

    Science.gov (United States)

    Van Acker, Thibaut; Van Malderen, Stijn J M; Van Heerden, Marjolein; McDuffie, James Eric; Cuyckens, Filip; Vanhaecke, Frank

    2016-11-16

    Two-dimensional elemental mapping (bioimaging) via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was performed on 5 μm thick formalin-fixed, paraffin-embedded kidney tissue sections from Cynomolgus monkeys administered with increasing pharmacological doses of cisplatin. Laterally resolved pixels of 1 μm were achieved, enabling elemental analysis on a (sub-)cellular level. Zones of high Pt response were observed in the renal cortex, where proximal tubules are present, the epithelium of which is responsible for partial reabsorption of cisplatin. Histopathological evaluation, of hematoxylin and eosin-stained serial sections, adjacent to the sections probed via LA-ICP-MS, revealed minimal to mild cisplatin-related lesions (<100 μm) in the renal cortex. Necrotic proximal tubules with sloughed epithelial cells in their lumen could be linked directly to the areas with the highest accumulation of cisplatin, indicating a direct link between cellular concentration and toxicity, thereby providing more insight into the mechanisms through which renal damage occurs.

  11. Characterisation of DEFB107 by mass spectrometry

    Science.gov (United States)

    McCullough, Bryan J.; Eastwood, Hayden; Clark, Dave J.; Polfer, Nick C.; Campopiano, Dominic J.; Dorin, Julia A.; Maxwell, Alison; Langley, Ross J.; Govan, John R. W.; Bernstein, Summer L.; Bowers, Michael T.; Barran, Perdita E.

    2006-05-01

    Mammalian defensins are small endogenous cationic proteins which form a class of antimicrobial peptides that is part of the innate immune response of all mammalian species [R. Lehrer, Nat. Rev. Microbiol. 2 (9) (2004) 727; T. Ganz, R.I. Lehrer, Curr. Opin. Immunol. 6 (4) (1994) 584] [1] and [2]. We have developed mass spectrometry based strategies for characterising the structure-activity relationship of defensins [D.J. Campopiano, D.J. Clarke, N.C. Polfer, P.E. Barran, R.J. Langley, J.R.W. Govan, A. Maxwell, J.R. Dorin, J. Biol. Chem. 279 (47) (2004) 48671; P.E. Barran, N.C. Polfer, D.J. Campopiano, D.J. Clarke, P.R.R. Langridge-Smith, R.J. Langley, J.R.W. Govan, A. Maxwell, J.R. Dorin, R.P. Millar, M.T. Bowers, Int. J. Mass Spectrom. 240 (2005) 273] [3] and [4], and here we present data obtained from a five cysteine containing [beta]-defensin, DEFB107. The synthetic product of this human defensin exists with a glutathione capping group, its oxidation state and disulphide connectivity have been determined via accurate mass measurements and peptide mass mapping respectively, and despite possessing three disulphide bridges, it does not fit the [beta]-defensin canonical motif. With the use of molecular modelling, we have generated candidate geometries to discern the influence of disulphide bridging on the overall tertiary structure of DEFB107. These are compared with experimental results from ion mobility measurements. Defensins display activity against a wide variety of pathogens including both gram-negative and gram-positive bacteria. Their mechanism of mode of action is unknown, but is believed to involve defensin aggregation at cell surfaces, followed by cell permeabilisation and hence deathE To probe this mechanism, the localisation of DEFB107 in synthetic vesicles was studied using H/D exchange and mass spectrometry. The results obtained are used to analyse the antimicrobial activity of DEFB107.

  12. Accelerator mass spectrometry (AMS) in plutonium analysis.

    Science.gov (United States)

    Strumińska-Parulska, Dagmara I

    The paper summarizes the results of the (240)Pu/(239)Pu atomic ratio studies in atmospheric fallout samples collected in 1986 over Gdynia (Poland) as well as three Baltic fish species collected in 1997 using the accelerator mass spectrometry. A new generation of AMS has been developed during last years and this method is an efficient and good technique to measure long-lived radioisotopes in the environment and provides the most accurate determination of the atomic ratios between (240)Pu and (239)Pu. The nuclide compositions of plutonium in filter samples correspond to their means of production. AMS measurements of atmospheric fallout collected in April showed sufficient increase of the (240)Pu/(239)Pu atomic ratio from 0.28 from March to 0.47. Also such high increase of (240)Pu/(239)Pu atomic ratio, close to reactor core (240)Pu/(239)Pu atomic ratio, was observed in September and equaled 0.47.

  13. Subattomole sensitivity in biological accelerator mass spectrometry.

    Science.gov (United States)

    Salehpour, Mehran; Possnert, Göran; Bryhni, Helge

    2008-05-15

    The Uppsala University 5 MV Pelletron tandem accelerator has been used to study (14)C-labeled biological samples utilizing accelerator mass spectrometry (AMS) technology. We have adapted a sample preparation method for small biological samples down to a few tens of micrograms of carbon, involving among others, miniaturizing of the graphitization reactor. Standard AMS requires about 1 mg of carbon with a limit of quantitation of about 10 amol. Results are presented for a range of small sample sizes with concentrations down to below 1 pM of a pharmaceutical substance in human blood. It is shown that (14)C-labeled molecular markers can be routinely measured from the femtomole range down to a few hundred zeptomole (10 (-21) mol), without the use of any additional separation methods.

  14. Mass spectrometry and Web 2.0.

    Science.gov (United States)

    Murray, Kermit K

    2007-10-01

    The term Web 2.0 is a convenient shorthand for a new era in the Internet in which users themselves are both generating and modifying existing web content. Several types of tools can be used. With social bookmarking, users assign a keyword to a web resource and the collection of the keyword 'tags' from multiple users form the classification of these resources. Blogs are a form of diary or news report published on the web in reverse chronological order and are a popular form of information sharing. A wiki is a website that can be edited using a web browser and can be used for collaborative creation of information on the site. This article is a tutorial that describes how these new ways of creating, modifying, and sharing information on the Web are being used for on-line mass spectrometry resources.

  15. Recent trends in inorganic mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Smith, D.H.; Barshick, C.M.; Duckworth, D.C.; Riciputi, L.R.

    1996-10-01

    The field of inorganic mass spectrometry has seen substantial change in the author`s professional lifetime (over 30 years). Techniques in their infancy 30 years ago have matured; some have almost disappeared. New and previously unthought of techniques have come into being; some of these, such as ICP-MS, are reasonably mature now, while others have some distance to go before they can be so considered. Most of these new areas provide fertile fields for researchers, both in the development of new analytical techniques and by allowing fundamental studies to be undertaken that were previously difficult, impossible, or completely unforeseen. As full coverage of the field is manifestly impossible within the framework of this paper, only those areas with which the author has personal contact will be discussed. Most of the work originated in his own laboratory, but that of other laboratories is covered where it seemed appropriate.

  16. Application of Nanodiamonds in Biomolecular Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Ping Cheng

    2010-03-01

    Full Text Available The combination of nanodiamond (ND with biomolecular mass spectrometry (MS makes rapid, sensitive detection of biopolymers from complex biosamples feasible. Due to its chemical inertness, optical transparency and biocompatibility, the advantage of NDs in MS study is unique. Furthermore, functionalization on the surfaces of NDs expands their application in the fields of proteomics and genomics for specific requirements greatly. This review presents methods of MS analysis based on solid phase extraction and elution on NDs and different application examples including peptide, protein, DNA, glycan and others. Owing to the quick development of nanotechnology, surface chemistry, new MS methods and the intense interest in proteomics and genomics, a huge increase of their applications in biomolecular MS analysis in the near future can be predicted.

  17. [Application of mass spectrometry in mycology].

    Science.gov (United States)

    Quiles Melero, Inmaculada; Peláez, Teresa; Rezusta López, Antonio; Garcia-Rodríguez, Julio

    2016-06-01

    MALDI-TOF (matrix-assisted laser desorption ionization time-of-flight) mass spectrometry (MS) is becoming an essential tool in most microbiology laboratories. At present, by using a characteristic fungal profile obtained from whole cells or through simple extraction protocols, MALDI-TOF MS allows the identification of pathogenic fungi with a high performance potential. This methodology decreases the laboratory turnaround time, optimizing the detection of mycoses. This article describes the state-of-the-art of the use of MALDI-TOF MS for the detection of human clinical fungal pathogens in the laboratory and discusses the future applications of this technology, which will further improve routine mycological diagnosis. Copyright © 2016 Elsevier España, S.L.U. All rights reserved.

  18. Mass Spectrometry Methodology in Lipid Analysis

    Directory of Open Access Journals (Sweden)

    Lin Li

    2014-06-01

    Full Text Available Lipidomics is an emerging field, where the structures, functions and dynamic changes of lipids in cells, tissues or body fluids are investigated. Due to the vital roles of lipids in human physiological and pathological processes, lipidomics is attracting more and more attentions. However, because of the diversity and complexity of lipids, lipid analysis is still full of challenges. The recent development of methods for lipid extraction and analysis and the combination with bioinformatics technology greatly push forward the study of lipidomics. Among them, mass spectrometry (MS is the most important technology for lipid analysis. In this review, the methodology based on MS for lipid analysis was introduced. It is believed that along with the rapid development of MS and its further applications to lipid analysis, more functional lipids will be identified as biomarkers and therapeutic targets and for the study of the mechanisms of disease.

  19. Glass microfabricated nebulizer chip for mass spectrometry.

    Science.gov (United States)

    Saarela, Ville; Haapala, Markus; Kostiainen, Risto; Kotiaho, Tapio; Franssila, Sami

    2007-05-01

    A microfluidic nebulizer chip for mass spectrometry is presented. It is an all-glass device which consists of fusion bonded Pyrex wafers with embedded flow channels and a nozzle at the chip edge. A platinum heater is located on the wafer backside. Fabrication of the chip is detailed, especially glass deep etching, wafer bonding, and metal patterning. Various process combinations of bonding and metallization have been considered (anodic bonding vs. fusion bonding; heater inside/outside channel; metallization before/after bonding; platinum lift-off vs. etching). The chip vaporizes the liquid sample (0.1-10 microL min(-1)) and mixes it with a nebulizer gas (ca. 100 sccm N2). Operating temperatures can go up to 500 degrees C ensuring efficient vaporization. Thermal insulation of the glass ensures low temperatures at the far end of the chip, enabling easy interconnections.

  20. Enantioselectivity of mass spectrometry: challenges and promises.

    Science.gov (United States)

    Awad, Hanan; El-Aneed, Anas

    2013-01-01

    With the fast growing market of pure enantiomer drugs and bioactive molecules, new chiral-selective analytical tools have been instigated including the use of mass spectrometry (MS). Even though MS is one of the best analytical tools that has efficiently been used in several pharmaceutical and biological applications, traditionally MS is considered as a "chiral-blind" technique. This limitation is due to the MS inability to differentiate between two enantiomers of a chiral molecule based merely on their masses. Several approaches have been explored to assess the potential role of MS in chiral analysis. The first approach depends on the use of MS-hyphenated techniques utilizing fast and sensitive chiral separation tools such as liquid chromatography (LC), gas chromatography (GC), and capillary electrophoresis (CE) coupled to MS detector. More recently, several alternative separation techniques have been evaluated such as supercritical fluid chromatography (SFC) and capillary electrochromatography (CEC); the latter being a hybrid technique that combines the efficiency of CE with the selectivity of LC. The second approach is based on using the MS instrument solely for the chiral recognition. This method depends on the behavioral differences between enantiomers towards a foreign molecule and the ability of MS to monitor such differences. These behavioral differences can be divided into three types: (i) differences in the enantiomeric affinity for association with the chiral selector, (ii) differences of the enantiomeric exchange rate with a foreign reagent, and (iii) differences in the complex MS dissociation behaviors of the enantiomers. Most recently, ion mobility spectrometry was introduced to qualitatively and quantitatively evaluate chiral compounds. This article provides an overview of MS role in chiral analysis by discussing MS based methodologies and presenting the challenges and promises associated with each approach.

  1. Low-Temperature Positive Secondary Ion Mass Spectrometry of Neat and Argon-Diluted Organic Solids

    NARCIS (Netherlands)

    Jonkman, Harry T.; Michl, Josef; King, Robert N.; Andrade, Joseph D.

    1978-01-01

    Secondary ion mass spectrometry of neat solid propane, n-pentane, benzene, toluene, and of propane imbedded in an argon matrix were observed at temperatures varying from 10 to 110 K and show fragmentation patterns similar to those known from ordinary electron impact mass spectrometry. The effects of

  2. Low-Temperature Positive Secondary Ion Mass Spectrometry of Neat and Argon-Diluted Organic Solids

    NARCIS (Netherlands)

    Jonkman, Harry T.; Michl, Josef; King, Robert N.; Andrade, Joseph D.

    1978-01-01

    Secondary ion mass spectrometry of neat solid propane, n-pentane, benzene, toluene, and of propane imbedded in an argon matrix were observed at temperatures varying from 10 to 110 K and show fragmentation patterns similar to those known from ordinary electron impact mass spectrometry. The effects of

  3. Advantageous Uses of Mass Spectrometry for the Quantification of Proteins

    Directory of Open Access Journals (Sweden)

    John E. Hale

    2013-01-01

    Full Text Available Quantitative protein measurements by mass spectrometry have gained wide acceptance in research settings. However, clinical uptake of mass spectrometric protein assays has not followed suit. In part, this is due to the long-standing acceptance by regulatory agencies of immunological assays such as ELISA assays. In most cases, ELISAs provide highly accurate, sensitive, relatively inexpensive, and simple assays for many analytes. The barrier to acceptance of mass spectrometry in these situations will remain high. However, mass spectrometry provides solutions to certain protein measurements that are difficult, if not impossible, to accomplish by immunological methods. Cases where mass spectrometry can provide solutions to difficult assay development include distinguishing between very closely related protein species and monitoring biological and analytical variability due to sample handling and very high multiplexing capacity. This paper will highlight several examples where mass spectrometry has made certain protein measurements possible where immunological techniques have had a great difficulty.

  4. Applications of accelerator mass spectrometry to nuclear physics and astrophysics

    CERN Document Server

    Guo, Z Y

    2002-01-01

    As an ultra high sensitive analyzing method, accelerator mass spectrometry is playing an important role in the studies of nuclear physics and astrophysics. The accelerator mass spectrometry (AMS) applications in searching for violation of Pauli exclusion principle and study on supernovae are discussed as examples

  5. From structure to function : Protein assemblies dissected by mass spectrometry

    NARCIS (Netherlands)

    Lorenzen, K.

    2008-01-01

    This thesis demonstrates some of the possibilities mass spectrometry can provide to gain new insight into structure and function of protein complexes. While technologies in native mass spectrometry are still under development, it already allows research on complete proteins and protein complexes up

  6. A quick, easy, cheap, effective, rugged, and safe sample pretreatment and liquid chromatography with tandem mass spectrometry method for the simultaneous quantification of 33 mycotoxins in Lentinula edodes.

    Science.gov (United States)

    Han, Zheng; Feng, Zhihong; Shi, Wen; Zhao, Zhihui; Wu, Yongjiang; Wu, Aibo

    2014-08-01

    Lentinula edodes, one of the most cultivated edible fungi in the world, are usually neglected for mycotoxins contamination due to the initial thinking of its resistance to mycotoxingenic molds. In the present study, a sensitive and reliable liquid chromatography with tandem mass spectrometry method was developed for the simultaneous quantification of 33 mycotoxins in L. edodes. Targeted mycotoxins were extracted using a quick, easy, cheap, effective, rugged, and safe procedure without any further clean-up step, and analyzed by liquid chromatography with tandem mass spectrometry on an Agilent Poroshell 120 EC-C18 column (100 × 3 mm, 2.7 μm) with a linear gradient elution program using water containing 5 mM ammonium acetate and methanol as the mobile phase. After validation by determining linearity (R(2) > 0.99), sensitivity (LOQ ≤ 20 ng/kg), recovery (73.6-117.9%), and precision (0.8-19.5%), the established method has been successfully applied to reveal the contamination states of various mycotoxins in L. edodes. Among the 30 tested samples, 22 were contaminated by various mycotoxins with the concentration levels ranging from 3.3-28,850.7 μg/kg, predicting that the edible fungus could be infected by the mycotoxins-producing fungi. To the best of our knowledge, this is the first report about real mycotoxins contamination in L. edodes.

  7. Clinical Mass Spectrometry: Achieving Prominence in Laboratory Medicine

    Energy Technology Data Exchange (ETDEWEB)

    Annesley, Thomas M.; Cooks, Robert G.; Herold, David A.; Hoofnagle, Andrew N.

    2016-01-04

    Each year the journal Clinical Chemistry publishes a January special issue on a topic that is relevant to the laboratory medicine community. In January 2016 the topic is mass spectrometry, and the issue is entitled “Clinical Mass Spectrometry: Achieving Prominence in Laboratory Medicine”. One popular feature in our issues is a Q&A on a topic, clearly in this case mass spectrometry. The journal is assembling a panel of 5-6 experts from various areas of mass spectrometry ranging from instrument manufacturing to practicing clinical chemists. Dick Smith is one of the scientist requested to participate in this special issue Q&A on Mass Spectrometry. The Q&A Transcript is attached

  8. History of mass spectrometry at the Olympic Games.

    Science.gov (United States)

    Hemmersbach, Peter

    2008-07-01

    Mass spectrometry has played a decisive role in doping analysis and doping control in human sport for almost 40 years. The standard of qualitative and quantitative determinations in body fluids has always attracted maximum attention from scientists. With its unique sensitivity and selectivity properties, mass spectrometry provides state-of-the-art technology in analytical chemistry. Both anti-doping organizations and the athletes concerned expect the utmost endeavours to prevent false-positive and false-negative results of the analytical evidence. The Olympic Games play an important role in international sport today and are milestones for technical development in doping analysis. This review of the part played by mass spectrometry in doping control from Munich 1972 to Beijing 2008 Olympics gives an overview of how doping analysis has developed and where we are today. In recognizing the achievements made towards effective doping control, it is of the utmost importance to applaud the joint endeavours of the World Anti-Doping Agency, the International Olympic Committee, the international federations and national anti-doping agencies to combat doping. Advances against the misuse of prohibited substances and methods, which are performance-enhancing, dangerous to health and violate the spirit of sport, can be achieved only if all the stakeholders work together.

  9. The effect of H2SO4 - amine clustering on chemical ionization mass spectrometry (CIMS) measurements of gas-phase sulfuric acid

    DEFF Research Database (Denmark)

    Kurten, T.; Petaja, T.; Smith, J.;

    2011-01-01

    by the CIMS instrument, though the most reliable computational methods employed predict this fraction to be small; on the order of ten percent or less. Third, the amine molecules will evaporate practically immediately after charging, thus evading detection. These effects may need to be taken into account......The state-of-the art method for measuring atmospheric gas-phase sulfuric acid is chemical ionization mass spectrometry (CIMS) based on nitrate reagent ions. We have assessed the possible effect of the sulfuric acid molecules clustering with base molecules on CIMS measurements using computational...... chemistry. From the computational data, three conclusions can be drawn. First, a significant fraction of the gas-phase sulfuric acid molecules are very likely clustered with amines if the amine concentration is around or above a few ppt. Second, some fraction of these acid-amine clusters may not be charged...

  10. Identification of Unknown Contaminants in Water Samples from ISS Employing Liquid Chromatography/Mass Spectrometry/Mass Spectrometry

    Science.gov (United States)

    Rutz, Jeffrey A.; Schultz, John R.

    2008-01-01

    Mass Spectrometry/Mass Spectrometry (MS/MS) is a powerful technique for identifying unknown organic compounds. For non-volatile or thermally unstable unknowns dissolved in liquids, liquid chromatography/mass spectrometry/mass spectrometry (LC/MS/MS) is often the variety of MS/MS used for the identification. One type of LC/MS/MS that is rapidly becoming popular is time-of-flight (TOF) mass spectrometry. This technique is now in use at the Johnson Space Center for identification of unknown nonvolatile organics in water samples from the space program. An example of the successful identification of one unknown is reviewed in detail in this paper. The advantages of time-of-flight instrumentation are demonstrated through this example as well as the strategy employed in using time-of-flight data to identify unknowns.

  11. Accelerator Mass Spectrometry in Laboratory Nuclear Astrophysics

    Science.gov (United States)

    Nusair, O.; Bauder, W.; Gyürky, G.; Paul, M.; Collon, P.; Fülöp, Zs; Greene, J.; Kinoshita, N.; Palchan, T.; Pardo, R.; Rehm, K. E.; Scott, R.; Vondrasek, R.

    2016-01-01

    The extreme sensitivity and discrimination power of accelerator mass spectrometry (AMS) allows for the search and the detection of rare nuclides either in natural samples or produced in the laboratory. At Argonne National Laboratory, we are developing an AMS setup aimed in particular at the detection of medium and heavy nuclides, relying on the high ion energy achievable with the ATLAS superconducting linear accelerator and on gas-filled magnet isobaric separation. The setup was recently used for the detection of the 146Sm p-process nuclide and for a new determination of the 146Sm half-life (68.7 My). AMS plays an important role in the measurement of stellar nuclear reaction cross sections by the activation method, extending thus the technique to the study of production of long-lived radionuclides. Preliminary measurements of the 147Sm(γ,n)146Sm are described. A measurement of the 142Nd(α,γ)146Sm and 142Nd(α,n)145Sm reactions is in preparation. A new laser-ablation method for the feeding of the Electron Cyclotron Resonance (ECR) ion source is described.

  12. Accelerator mass spectrometry of small biological samples.

    Science.gov (United States)

    Salehpour, Mehran; Forsgard, Niklas; Possnert, Göran

    2008-12-01

    Accelerator mass spectrometry (AMS) is an ultra-sensitive technique for isotopic ratio measurements. In the biomedical field, AMS can be used to measure femtomolar concentrations of labeled drugs in body fluids, with direct applications in early drug development such as Microdosing. Likewise, the regenerative properties of cells which are of fundamental significance in stem-cell research can be determined with an accuracy of a few years by AMS analysis of human DNA. However, AMS nominally requires about 1 mg of carbon per sample which is not always available when dealing with specific body substances such as localized, organ-specific DNA samples. Consequently, it is of analytical interest to develop methods for the routine analysis of small samples in the range of a few tens of microg. We have used a 5 MV Pelletron tandem accelerator to study small biological samples using AMS. Different methods are presented and compared. A (12)C-carrier sample preparation method is described which is potentially more sensitive and less susceptible to contamination than the standard procedures.

  13. Detection of Gunshot Residues Using Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Regina Verena Taudte

    2014-01-01

    Full Text Available In recent years, forensic scientists have become increasingly interested in the detection and interpretation of organic gunshot residues (OGSR due to the increasing use of lead- and heavy metal-free ammunition. This has also been prompted by the identification of gunshot residue- (GSR- like particles in environmental and occupational samples. Various techniques have been investigated for their ability to detect OGSR. Mass spectrometry (MS coupled to a chromatographic system is a powerful tool due to its high selectivity and sensitivity. Further, modern MS instruments can detect and identify a number of explosives and additives which may require different ionization techniques. Finally, MS has been applied to the analysis of both OGSR and inorganic gunshot residue (IGSR, although the “gold standard” for analysis is scanning electron microscopy with energy dispersive X-ray microscopy (SEM-EDX. This review presents an overview of the technical attributes of currently available MS and ionization techniques and their reported applications to GSR analysis.

  14. Secondary Ion Mass Spectrometry SIMS XI

    Science.gov (United States)

    Gillen, G.; Lareau, R.; Bennett, J.; Stevie, F.

    2003-05-01

    This volume contains 252 contributions presented as plenary, invited and contributed poster and oral presentations at the 11th International Conference on Secondary Ion Mass Spectrometry (SIMS XI) held at the Hilton Hotel, Walt Disney World Village, Orlando, Florida, 7 12 September, 1997. The book covers a diverse range of research, reflecting the rapid growth in advanced semiconductor characterization, ultra shallow depth profiling, TOF-SIMS and the new areas in which SIMS techniques are being used, for example in biological sciences and organic surface characterization. Papers are presented under the following categories: Isotopic SIMS Biological SIMS Semiconductor Characterization Techniques and Applications Ultra Shallow Depth Profiling Depth Profiling Fundamental/Modelling and Diffusion Sputter-Induced Topography Fundamentals of Molecular Desorption Organic Materials Practical TOF-SIMS Polyatomic Primary Ions Materials/Surface Analysis Postionization Instrumentation Geological SIMS Imaging Fundamentals of Sputtering Ion Formation and Cluster Formation Quantitative Analysis Environmental/Particle Characterization Related Techniques These proceedings provide an invaluable source of reference for both newcomers to the field and experienced SIMS users.

  15. Tandem mass spectrometry: analysis of complex mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Singleton, K.E.

    1985-01-01

    Applications of tandem mass spectrometry (MS/MS) for the analysis of complex mixtures results in increased specificity and selectivity by using a variety of reagent gases in both negative and positive ion modes. Natural isotopic abundance ratios were examined in both simple and complex mixtures using parent, daughter and neutral loss scans. MS/MS was also used to discover new compounds. Daughter scans were used to identify seven new alkaloids in a cactus species. Three of these alkaloids were novel compounds, and included the first simple, fully aromatic isoquinoline alkaloids reported in Cactaceae. MS/MS was used to characterize the chemical reaction products of coal in studies designed to probe its macromolecular structure. Negative ion chemical ionization was utilized to study reaction products resulting from the oxidation of coal. Possible structural units in the precursor coal were predicted based on the reaction products identified, aliphatic and aromatic acids and their anhydrides. The MS/MS method was also used to characterize reaction products resulting from coal liquefaction and/or extraction. These studies illustrate the types of problems for which MS/MS is useful. Emphasis has been placed on characterization of complex mixtures by selecting experimental parameters which enhance the information obtained. The value of using MS/MS in conjunction with other analytical techniques as well as the chemical pretreatment is demonstrated.

  16. Proton Dynamics in Protein Mass Spectrometry.

    Science.gov (United States)

    Li, Jinyu; Lyu, Wenping; Rossetti, Giulia; Konijnenberg, Albert; Natalello, Antonino; Ippoliti, Emiliano; Orozco, Modesto; Sobott, Frank; Grandori, Rita; Carloni, Paolo

    2017-02-22

    Native electrospray ionization/ion mobility-mass spectrometry (ESI/IM-MS) allows an accurate determination of low-resolution structural features of proteins. Yet, the presence of proton dynamics, observed already by us for DNA in the gas phase, and its impact on protein structural determinants, have not been investigated so far. Here, we address this issue by a multistep simulation strategy on a pharmacologically relevant peptide, the N-terminal residues of amyloid-β peptide (Aβ(1-16)). Our calculations reproduce the experimental maximum charge state from ESI-MS and are also in fair agreement with collision cross section (CCS) data measured here by ESI/IM-MS. Although the main structural features are preserved, subtle conformational changes do take place in the first ∼0.1 ms of dynamics. In addition, intramolecular proton dynamics processes occur on the picosecond-time scale in the gas phase as emerging from quantum mechanics/molecular mechanics (QM/MM) simulations at the B3LYP level of theory. We conclude that proton transfer phenomena do occur frequently during fly time in ESI-MS experiments (typically on the millisecond time scale). However, the structural changes associated with the process do not significantly affect the structural determinants.

  17. MSSimulator: Simulation of mass spectrometry data.

    Science.gov (United States)

    Bielow, Chris; Aiche, Stephan; Andreotti, Sandro; Reinert, Knut

    2011-07-01

    Mass spectrometry coupled to liquid chromatography (LC-MS and LC-MS/MS) is commonly used to analyze the protein content of biological samples in large scale studies, enabling quantitation and identification of proteins and peptides using a wide range of experimental protocols, algorithms, and statistical models to analyze the data. Currently it is difficult to compare the plethora of algorithms for these tasks. So far, curated benchmark data exists for peptide identification algorithms but data that represents a ground truth for the evaluation of LC-MS data is limited. Hence there have been attempts to simulate such data in a controlled fashion to evaluate and compare algorithms. We present MSSimulator, a simulation software for LC-MS and LC-MS/MS experiments. Starting from a list of proteins from a FASTA file, the simulation will perform in-silico digestion, retention time prediction, ionization filtering, and raw signal simulation (including MS/MS), while providing many options to change the properties of the resulting data like elution profile shape, resolution and sampling rate. Several protocols for SILAC, iTRAQ or MS(E) are available, in addition to the usual label-free approach, making MSSimulator the most comprehensive simulator for LC-MS and LC-MS/MS data.

  18. Charging of Proteins in Native Mass Spectrometry

    Science.gov (United States)

    Susa, Anna C.; Xia, Zijie; Tang, Henry Y. H.; Tainer, John A.; Williams, Evan R.

    2017-02-01

    Factors that influence the charging of protein ions formed by electrospray ionization from aqueous solutions in which proteins have native structures and function were investigated. Protein ions ranging in molecular weight from 12.3 to 79.7 kDa and pI values from 5.4 to 9.6 were formed from different solutions and reacted with volatile bases of gas-phase basicities higher than that of ammonia in the cell of a Fourier-transform ion cyclotron resonance mass spectrometer. The charge-state distribution of cytochrome c ions formed from aqueous ammonium or potassium acetate is the same. Moreover, ions formed from these two solutions do not undergo proton transfer to 2-fluoropyridine, which is 8 kcal/mol more basic than ammonia. These results provide compelling evidence that proton transfer between ammonia and protein ions does not limit protein ion charge in native electrospray ionization. Both circular dichroism and ion mobility measurements indicate that there are differences in conformations of proteins in pure water and aqueous ammonium acetate, and these differences can account for the difference in the extent of charging and proton-transfer reactivities of protein ions formed from these solutions. The extent of proton transfer of the protein ions with higher gas-phase basicity bases trends with how closely the protein ions are charged to the value predicted by the Rayleigh limit for spherical water droplets approximately the same size as the proteins. These results indicate that droplet charge limits protein ion charge in native mass spectrometry and are consistent with these ions being formed by the charged residue mechanism.

  19. Effects of drift gas on collision cross sections of a protein standard in linear drift tube and traveling wave ion mobility mass spectrometry.

    Science.gov (United States)

    Jurneczko, Ewa; Kalapothakis, Jason; Campuzano, Iain D G; Morris, Michael; Barran, Perdita E

    2012-10-16

    There has been a significant increase in the use of ion mobility mass spectrometry (IM-MS) to investigate conformations of proteins and protein complexes following electrospray ionization. Investigations which employ traveling wave ion mobility mass spectrometry (TW IM-MS) instrumentation rely on the use of calibrants to convert the arrival times of ions to collision cross sections (CCS) providing "hard numbers" of use to structural biology. It is common to use nitrogen as the buffer gas in TW IM-MS instruments and to calibrate by extrapolating from CCS measured in helium via drift tube (DT) IM-MS. In this work, both DT and TW IM-MS instruments are used to investigate the effects of different drift gases (helium, neon, nitrogen, and argon) on the transport of multiply charged ions of the protein myoglobin, frequently used as a standard in TW IM-MS studies. Irrespective of the drift gas used, recorded mass spectra are found to be highly similar. In contrast, the recorded arrival time distributions and the derived CCS differ greatly. At low charge states (7 ≤ z ≤ 11) where the protein is compact, the CCS scale with the polarizability of the gas; this is also the case for higher charge states (12 ≤ z ≤ 22) where the protein is more unfolded for the heavy gases (neon, argon, and nitrogen) but not the case for helium. This is here interpreted as a different conformational landscape being sampled by the lighter gas and potentially attributable to increased field heating by helium. Under nanoelectrospray ionization (nESI) conditions, where myoglobin is sprayed from an aqueous solution buffered to pH 6.8 with 20 mM ammonium acetate, in the DT IM-MS instrument, each buffer gas can yield a different arrival time distribution (ATD) for any given charge state.

  20. Interpretation of Tandem Mass Spectrometry (MSMS) Spectra for Peptide Analysis

    DEFF Research Database (Denmark)

    Hjernø, Karin; Højrup, Peter

    2015-01-01

    The aim of this chapter is to give a short introduction to peptide analysis by mass spectrometry (MS) and interpretation of fragment mass spectra. Through examples and guidelines we demonstrate how to understand and validate search results and how to perform de novo sequencing based on the often...... very complex fragmentation pattern obtained by tandem mass spectrometry (also referred to as MSMS). The focus is on simple rules for interpretation of MSMS spectra of tryptic as well as non-tryptic peptides....

  1. Plutonium measurements by accelerator mass spectrometry at LLNL

    Energy Technology Data Exchange (ETDEWEB)

    McAninch, J E; Hamilton, T F; Broan, T A; Jokela, T A; Knezovich, T J; Ognibene, T J; Proctor, I D; Roberts, M L; Southon, J R; Vogel, J S; Sideras-Haddad, E

    1999-10-26

    Mass spectrometric methods provide sensitive, routine, and cost-effective analyses of long-lived radionuclides. Here the authors report on the status of work at Lawrence Livermore National Laboratory (LLNL) to develop a capability for actinide measurements by accelerator mass spectrometry (AMS) to take advantage of the high potential of AMS for rejection of interferences. This work demonstrates that the LLNL AMS spectrometer is well-suited for providing high sensitivity, robust, high throughput measurements of plutonium concentrations and isotope ratios. Present backgrounds are {approximately}2 x 10{sup 7}atoms per sample for environmental samples prepared using standard alpha spectrometry protocols. Recent measurements of {sup 239+240}Pu and {sup 241}Pu activities and {sup 240}Pu/{sup 239}Pu isotope ratios in IAEA reference materials agree well with IAEA reference values and with alpha spectrometry and recently published ICP-MS results. Ongoing upgrades of the AMS spectrometer are expected to reduce backgrounds below 1 x 10{sup 6} atoms per sample while allowing simplifications of the sample preparation chemistry. These simplifications will lead to lower per-sample costs, higher throughput, faster turn around and, ultimately, to larger and more robust data sets.

  2. Metabolic profiling of asthma in mice and the interventional effects of SPA using liquid chromatography and Q-TOF mass spectrometry.

    Science.gov (United States)

    Su, Li; Shi, Lei; Liu, Jian; Huang, Lifei; Huang, Yi; Nie, Xiaomeng

    2017-05-30

    Asthma is a chronic inflammatory lung disease that leads to 250 000 deaths annually. There is a need to better understand asthma by identifying new pathogenic molecules. We conducted a liquid-chromatography time-of-flight mass spectrometry (LC-Q-TOF-MS)-based metabolomics study to test for asthma and investigate the interventional mechanisms of surfactant protein A (SPA) in OVA-induced asthma mice. The results revealed that asthma disturbed 32 metabolites in 9 metabolic pathways. After SPA treatment, the metabolomics profile found in asthma was significantly reversed, shifting much closer to that of the control group, indicating that SPA has therapeutic effects against asthma. Metabolomic pathway analysis by the ingenuity pathway analysis demonstrated that several pathways including fatty acid metabolism, lipid metabolism, and purine metabolism were significantly altered in asthma. This study offers new methodologies for the understanding of asthma and the mechanisms of SPA in treating asthma.

  3. Dehydrodimerization of pterostilbene during electrospray ionization mass spectrometry

    KAUST Repository

    Raji, Misjudeen

    2013-04-30

    RATIONALE Pterostilbene is a member of the hydroxystilbene family of compounds commonly found in plants such as blueberry and grapes. During the analysis of this compound by electrospray ionization mass spectrometry (ESI-MS), an ion was observed that corresponds to the dehydrodimer of pterostilbene in mass-to-charge ratio. Since such unexpected dimerization may lead to decreased monomer signal during quantitative analysis, it was of interest to identify the origin and structure of the observed pterostilbene dimer and examine the experimental conditions that influence its formation. METHODS Liquid Chromatography/Mass Spectrometry (LC/MS), Nuclear Magnetic Resonance (NMR), and High-Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) were used to examine the origin of the dimerization products. The structure of the formed pterostilbene dimer was examined by performing MSn analysis on the dimer ion. Effects of solvent composition, analyte concentration, radical scavenger, and other experimental conditions on the dimerization were also studied. RESULTS LC/MS and NMR analyses clearly showed that the starting solution did not contain the pterostilbene dimer. Solvent type and radical scavenger concentration were found to have pronounced effects on the dimer formation. Particularly, presence of acetonitrile or ammonium acetate had favorable effects on the extent of dimerization during ESI-MS analysis whereas hydroquinone and butylated hydroquinone had negative effects. Dimer formation decreased at high flow rates and when fused-silica capillary was used as the spray needle. CONCLUSIONS The data indicate that this dimerization occurs as a result of solution-phase electrochemical reactions taking place during the electrospray process. A possible structure for this dimer was proposed based on the MSn analysis and was similar to that of the enzymatically derived pterostilbene dehydrodimer already reported in the literature. Copyright © 2013 John Wiley & Sons, Ltd

  4. Fourier transform ion cyclotron resonance mass spectrometry: a primer.

    Science.gov (United States)

    Marshall, A G; Hendrickson, C L; Jackson, G S

    1998-01-01

    This review offers an introduction to the principles and generic applications of FT-ICR mass spectrometry, directed to readers with no prior experience with the technique. We are able to explain the fundamental FT-ICR phenomena from a simplified theoretical treatment of ion behavior in idealized magnetic and electric fields. The effects of trapping voltage, trap size and shape, and other nonidealities are manifested mainly as perturbations that preserve the idealized ion behavior modified by appropriate numerical correction factors. Topics include: effect of ion mass, charge, magnetic field, and trapping voltage on ion cyclotron frequency; excitation and detection of ICR signals; mass calibration; mass resolving power and mass accuracy; upper mass limit(s); dynamic range; detection limit, strategies for mass and energy selection for MSn; ion axialization, cooling, and remeasurement; and means for guiding externally formed ions into the ion trap. The relation of FT-ICR MS to other types of Fourier transform spectroscopy and to the Paul (quadrupole) ion trap is described. The article concludes with selected applications, an appendix listing accurate fundamental constants needed for ultrahigh-precision analysis, and an annotated list of selected reviews and primary source publications that describe in further detail various FT-ICR MS techniques and applications.

  5. Mass spectrometry for characterizing plant cell wall polysaccharides

    Directory of Open Access Journals (Sweden)

    Stefan eBauer

    2012-03-01

    Full Text Available Mass spectrometry is a selective and powerful technique to obtain identification and structural information on compounds present in complex mixtures. Since it requires only small sample amount it is an excellent tool for researchers interested in detecting changes in composition of complex carbohydrates of plants. This mini-review gives an overview of common mass spectrometry techniques applied to the analysis of plant cell wall carbohydrates. It presents examples in which mass spectrometry has been used to elucidate the structure of oligosaccharides derived from hemicelluloses and pectins and illustrates how information on sequence, linkages, branching and modifications are obtained from characteristic fragmentation patterns.

  6. The Vanderbilt Mass Spectrometry Shared Facilities

    Science.gov (United States)

    Friedman, D.B.; Reyzer, M.L.; Seeley, E.H.; Calcutt, M. Wade; Hachey, D.L.; Caprioli, R.M.; McDonald, W.H.

    2010-01-01

    CF-33 The Vanderbilt Mass Spectrometry Research Center (MSRC) provides an integrated bioanalytical service facility to Vanderbilt researchers coupled with a strong MS research component.The synergies achieved by merging research and service provide investigators with state-of-the-art proteomics, tissue profiling/imaging, and bioanalytical MS technologies. These cores are managed by a professional staff of six faculty members and five research assistants, bioinformatics specialists, and an instrument engineer. The Proteomics Laboratory supports multiple technology platforms, including HPLC peptide separations and 2D gel separations of intact proteins. Analysis can be performed by ESI-linear ion trap/orbitrap and MALDI-TOF/TOF MS with all of the necessary downstream bioinformatics for protein identification and characterization. We routinely utilize single- and multi-dimensional LC/MS/MS for protein cataloguing and differential-expression studies (using spectral counting), and Difference Gel Electrophoresis (DIGE) for large-scale expression studies on complex proteomes. The Tissue Imaging core provides tissue sectioning, staining, and MS directly from tissue sections via either high resolution imaging across an entire tissue section, or higher-throughput histology-directed profiling using specific tissue areas.As with the proteomics analysis, the necessary tools and infrastructure are available for downstream biostatistical analysis of the MS data. Both of these cores work closely with users at all stages of experiments including detailed informatics consultations and training. They generally operate as limited-access facilities where users prepare samples and core technical staff performs the analyses. The Bioanalytical MS Core provides instrumentation to perform a wide variety of analyses (e.g. identification and structural analysis of biological molecules, and qualitative and quantitative assays of drugs and metabolites). The MS Core operates in an open access

  7. A Review on Mass Spectrometry: Technique and Tools

    Directory of Open Access Journals (Sweden)

    Ms. Ashwini Yerlekar

    2014-04-01

    Full Text Available Protein structure prediction has gain important in area of life sciences, because of its complex structure. The protein-protein interaction is necessary to study the behavior of protein in a specific environment, and study molecular relationship in living systems. Therefore, large scale proteomics technologies are required to measure physical connection of proteins in living organisms. Mass Spectrometry uses the technique to measure mass-to-charge ratio of ion. It's an evolving technique for characterization of proteins. A Mass Spectrometer can be more sensitive and specific, also complement with other LC detectors. Liquid Chromatography, unlike gas chromatography is a separation technique which helps to separate wide range of organic compounds from small molecular metabolites to peptides and proteins. This paper addresses the study of data analysis using mass Spectrometry. It also includes the study of various methods of Mass Spectrometry data analysis, the tools and various applications of Mass Spectrometry.This review briefs on Mass Spectrometry technique, its application, usage, and tools used by Mass Spectrometry

  8. Constraining Anthropogenic and Biogenic Emissions Using Chemical Ionization Mass Spectrometry

    Science.gov (United States)

    Spencer, Kathleen M.

    Numerous gas-phase anthropogenic and biogenic compounds are emitted into the atmosphere. These gases undergo oxidation to form other gas-phase species and particulate matter. Whether directly or indirectly, primary pollutants, secondary gas-phase products, and particulate matter all pose health and environmental risks. In this work, ambient measurements conducted using chemical ionization mass spectrometry are used as a tool for investigating regional air quality. Ambient measurements of peroxynitric acid (HO2NO2) were conducted in Mexico City. A method of inferring the rate of ozone production, PO3, is developed based on observations of HO2NO 2, NO, and NO2. Comparison of this observationally based PO3 to a highly constrained photochemical box model indicates that regulations aimed at reducing ozone levels in Mexico City by reducing NOx concentrations may be effective at higher NO x levels than predicted using accepted photochemistry. Measurements of SO2 and particulate sulfate were conducted over the Los Angeles basin in 2008 and are compared to measurements made in 2002. A large decrease in SO2 concentration and a change in spatial distribution are observed. Nevertheless, only a modest reduction in sulfate concentration is observed at ground sites within the basin. Possible explanations for these trends are investigated. Two techniques, single and triple quadrupole chemical ionization mass spectrometry, were used to quantify ambient concentrations of biogenic oxidation products, hydroxyacetone and glycolaldehyde. The use of these techniques demonstrates the advantage of triple quadrupole mass spectrometry for separation of mass analogues, provided the collision-induced daughter ions are sufficiently distinct. Enhancement ratios of hydroxyacetone and glycolaldehyde in Californian biomass burning plumes are presented as are concentrations of these compounds at a rural ground site downwind of Sacramento.

  9. Analysis of fluticasone propionate in induced sputum by mass spectrometry.

    Science.gov (United States)

    Hagan, John B; Taylor, Robert L; Kita, Hirohito; Singh, Ravinder J

    2011-01-01

    Although evaluation of induced sputum has shown promise as a marker of eosinophilic airway inflammation in asthmatic subjects, most studies, to date, do not adequately address the potential effect that inhaled corticosteroids may have on sputum eosinophilia. This study was designed to prospectively evaluate analysis of fluticasone propionate (FP) in whole sputum by mass spectrometry as a tool to determine recent administration of inhaled FP. Induced sputum of nonsmoking asthmatic subjects was prospectively analyzed 16-24 hours after witnessed administration of orally inhaled FP. FP was extracted from whole sputum via an acetonitrile protein precipitation followed by methylene chloride liquid extraction of the supernatant (AB 4000; AB Sciex). A portion of the reconstituted sample was analyzed by liquid chromatography tandem mass spectrometry using a triple quad tandem mass spectrometer. Results were compared with those from nonsmoking asthmatic subjects not receiving inhaled FP. Twenty-two asthmatic subjects on FP and 9 asthmatic subjects without FP underwent sputum induction 16-24 hours following witnessed administration of FP. Sufficient sputum for analysis was obtained from 30 of 31 subjects. FP was detected in 22 of 22 asthmatic subjects receiving FP (range, 29-133,000 pg/mL) and was undetectable in 8 of 8 subjects not receiving FP. The sensitivity and specificity of tandem mass spectrometry's ability to detect FP in sputum was 100% and 100%, respectively. Analysis of FP in induced sputum is a reliable method to verify recent administration of inhaled FP. Induced asthmatic sputum from one induction may be used to concomitantly assess sputum eosinophilia as well as recent administration of FP.

  10. Application of accelerator mass spectrometry in aluminum metabolism studies

    Science.gov (United States)

    Meirav, O.; Sutton, R. A. L.; Fink, D.; Middleton, R.; Klein, J.; Walker, V. R.; Halabe, A.; Vetterli, D.; Johnson, R. R.

    1990-12-01

    The recent recognition that aluminum causes toxicity in uremie patients and may be associated with Alzheimer's disease has stimulated many studies of its biochemical effects. However, such studies were hampered by the lack of a suitable tracer. In a novel experiment, we have applied the new technique of accelerator mass spectrometry to investigate aluminum kinetics in rats, using as a marker the long-lived isotope 26Al. We present the first aluminum kinetic model for a biological system. The results clearly demonstrate the advantage this technique holds for isotope tracer studies in animals as well as in humans.

  11. Effect of heating strategies on whey protein denaturation--Revisited by liquid chromatography quadrupole time-of-flight mass spectrometry.

    Science.gov (United States)

    Akkerman, M; Rauh, V M; Christensen, M; Johansen, L B; Hammershøj, M; Larsen, L B

    2016-01-01

    Previous standards in the area of effect of heat treatment processes on milk protein denaturation were based primarily on laboratory-scale analysis and determination of denaturation degrees by, for example, electrophoresis. In this study, whey protein denaturation was revisited by pilot-scale heating strategies and liquid chromatography quadrupole time-of-flight mass spectrometer (LC/MC Q-TOF) analysis. Skim milk was heat treated by the use of 3 heating strategies, namely plate heat exchanger (PHE), tubular heat exchanger (THE), and direct steam injection (DSI), under various heating temperatures (T) and holding times. The effect of heating strategy on the degree of denaturation of β-lactoglobulin and α-lactalbumin was determined using LC/MC Q-TOF of pH 4.5-soluble whey proteins. Furthermore, effect of heating strategy on the rennet-induced coagulation properties was studied by oscillatory rheometry. In addition, rennet-induced coagulation of heat-treated micellar casein concentrate subjected to PHE was studied. For skim milk, the whey protein denaturation increased significantly as T and holding time increased, regardless of heating method. High denaturation degrees were obtained for T >100°C using PHE and THE, whereas DSI resulted in significantly lower denaturation degrees, compared with PHE and THE. Rennet coagulation properties were impaired by increased T and holding time regardless of heating method, although DSI resulted in less impairment compared with PHE and THE. No significant difference was found between THE and PHE for effect on rennet coagulation time, whereas the curd firming rate was significantly larger for THE compared with PHE. Micellar casein concentrate possessed improved rennet coagulation properties compared with skim milk receiving equal heat treatment.

  12. Application of Lithium Attachment Mass Spectrometry for Knudsen Evaporation and Chemical Ionisation Mass Spectrometry (KEMS, CIMS)

    Science.gov (United States)

    Bannan, Thomas; Booth, A. Murray; Alfarra, Rami; Bacak, Asan; Pericval, Carl

    2016-04-01

    Lithium ion attachment mass spectrometry provides a non-specific, non-fragmenting and sensitive method for detection of volatile species in the gas phase. The design, manufacture, and results from lithium ion attachment ionisation sources for two mass spectrometry systems are presented. Trace gas analysis is investigated using a modified Chemical Ionization Mass Spectrometer (CIMS) and vapour pressure (VP) measurements using a modified Knudsen Effusion Mass Spectrometer (KEMS) are presented. The Li+ modified CIMS provided limits of detection of 4 ppt for acetone, 0.2 ppt for formic acid, 15 ppt for nitric acid and 120 ppt from ammonia. Despite improvements, the problem of burnout remained persistent. The Li+ CIMS would unlikely be suitable for field or aircraft work, but could be appropriate for certain lab applications. The KEMS currently utilizes an electron impact (EI) ionisation source which provides a highly sensitive source, with the drawback of fragmentation of ionized molecules (Booth et al., 2009). Using Li+ KEMS the VP of samples can be measured without fragmentation and can therefore be used to identify VPs of individual components in mixtures. The validity of using Li+ for determining the VP of mixtures was tested by making single component VP measurements, which showed good agreement with EI measurements of Poly ethylene glycol (PEG) 3 and PEG 4, both when individually measured and when mixed. The Li+ KEMS was then used to investigate a system of atmospheric relevance, α-pinene secondary organic aerosol, generated in a reaction chamber (Alfarra et al., 2012). The VPs of the individual components from this generated sample are within the range we expect for compounds capable of partitioning between the particle and gas phase of an aerosol (0.1-10-5 Pa). Li+ source has a calculated sensitivity approximately 75 times less than that of EI, but the lack of fragmentation using the Li+ source is a significant advantage.

  13. imzML: Imaging Mass Spectrometry Markup Language: A common data format for mass spectrometry imaging.

    Science.gov (United States)

    Römpp, Andreas; Schramm, Thorsten; Hester, Alfons; Klinkert, Ivo; Both, Jean-Pierre; Heeren, Ron M A; Stöckli, Markus; Spengler, Bernhard

    2011-01-01

    Imaging mass spectrometry is the method of scanning a sample of interest and generating an "image" of the intensity distribution of a specific analyte. The data sets consist of a large number of mass spectra which are usually acquired with identical settings. Existing data formats are not sufficient to describe an MS imaging experiment completely. The data format imzML was developed to allow the flexible and efficient exchange of MS imaging data between different instruments and data analysis software.For this purpose, the MS imaging data is divided in two separate files. The mass spectral data is stored in a binary file to ensure efficient storage. All metadata (e.g., instrumental parameters, sample details) are stored in an XML file which is based on the standard data format mzML developed by HUPO-PSI. The original mzML controlled vocabulary was extended to include specific parameters of imaging mass spectrometry (such as x/y position and spatial resolution). The two files (XML and binary) are connected by offset values in the XML file and are unambiguously linked by a universally unique identifier. The resulting datasets are comparable in size to the raw data and the separate metadata file allows flexible handling of large datasets.Several imaging MS software tools already support imzML. This allows choosing from a (growing) number of processing tools. One is no longer limited to proprietary software, but is able to use the processing software which is best suited for a specific question or application. On the other hand, measurements from different instruments can be compared within one software application using identical settings for data processing. All necessary information for evaluating and implementing imzML can be found at http://www.imzML.org .

  14. VACUUM DISTILLATION COUPLED WITH GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR THE ANALYSIS OF ENVIRONMENTAL SAMPLES

    Science.gov (United States)

    A procedure is presented that uses a vacuum distillation/gas chromatography/mass spectrometry system for analysis of problematic matrices of volatile organic compounds. The procedure compensates for matrix effects and provides both analytical results and confidence intervals from...

  15. Laser mass spectrometry for DNA sequencing, disease diagnosis, and fingerprinting

    Energy Technology Data Exchange (ETDEWEB)

    Winston Chen, C.H.; Taranenko, N.I.; Zhu, Y.F.; Chung, C.N.; Allman, S.L.

    1997-03-01

    Since laser mass spectrometry has the potential for achieving very fast DNA analysis, the authors recently applied it to DNA sequencing, DNA typing for fingerprinting, and DNA screening for disease diagnosis. Two different approaches for sequencing DNA have been successfully demonstrated. One is to sequence DNA with DNA ladders produced from Snager`s enzymatic method. The other is to do direct sequencing without DNA ladders. The need for quick DNA typing for identification purposes is critical for forensic application. The preliminary results indicate laser mass spectrometry can possibly be used for rapid DNA fingerprinting applications at a much lower cost than gel electrophoresis. Population screening for certain genetic disease can be a very efficient step to reducing medical costs through prevention. Since laser mass spectrometry can provide very fast DNA analysis, the authors applied laser mass spectrometry to disease diagnosis. Clinical samples with both base deletion and point mutation have been tested with complete success.

  16. Effect-directed analysis of cold-pressed hemp, flax and canola seed oils by planar chromatography linked with (bio)assays and mass spectrometry.

    Science.gov (United States)

    Teh, Sue-Siang; Morlock, Gertrud E

    2015-11-15

    Cold-pressed hemp, flax and canola seed oils are healthy oils for human consumption as these are rich in polyunsaturated fatty acids and bioactive phytochemicals. However, bioactive information on the food intake side is mainly focused on target analysis. For more comprehensive information with regard to effects, single bioactive compounds present in the seed oil extracts were detected by effect-directed assays, like bioassays or an enzymatic assay, directly linked with chromatography and further characterized by mass spectrometry. This effect-directed analysis is a streamlined method for the analysis of bioactive compounds in the seed oil extracts. All effective compounds with regard to the five assays or bioassays applied were detected in the samples, meaning also bioactive breakdown products caused during oil processing, residues or contaminants, aside the naturally present bioactive phytochemicals. The investigated cold-pressed oils contained compounds that exert antioxidative, antimicrobial, acetylcholinesterase inhibitory and estrogenic activities. This effect-directed analysis can be recommended for bioactivity profiling of food to obtain profound effect-directed information on the food intake side.

  17. "Meta Elimination," a Diagnostic Fragmentation in Mass Spectrometry

    Science.gov (United States)

    Attygalle, Athula B.; Nishshanka, Upul; Weisbecker, Carl S.

    2011-09-01

    The diagnostic value of the "ortho effect" for unknown identification by mass spectrometry is well known. Here, we report the existence of a novel "meta effect," which adds to the repertoire of useful mass spectrometric fragmentation mechanisms. For example, the meta-specific elimination pathway described in this report enables unequivocal identification of meta isomers from ortho and para isomers of carboxyanilides. The reaction follows a specific path to eliminate a molecule of meta-benzyne, from the anion produced after the initial decarboxylation of the precursor. Consequently, in the CID spectra of carboxyanilides, a peak for the (R-CO-NH)- anion is observed only for the meta isomers. For example, the peaks observed at m/z 58, 86, 120, 128, and 170 from acetamido-, butamido-, benzamido, heptamido-, and decanamido-benzoates, respectively, were specific only to the spectra of meta isomers.

  18. Analysis of chirality by femtosecond laser ionization mass spectrometry.

    Science.gov (United States)

    Horsch, Philipp; Urbasch, Gunter; Weitzel, Karl-Michael

    2012-09-01

    Recent progress in the field of chirality analysis employing laser ionization mass spectrometry is reviewed. Emphasis is given to femtosecond (fs) laser ionization work from the author's group. We begin by reviewing fundamental aspects of determining circular dichroism (CD) in fs-laser ionization mass spectrometry (fs-LIMS) discussing an example from the literature (resonant fs-LIMS of 3-methylcyclopentanone). Second, we present new data indicating CD in non-resonant fs-LIMS of propylene oxide.

  19. Yeast expression proteomics by high-resolution mass spectrometry

    DEFF Research Database (Denmark)

    Walther, Tobias C; Olsen, Jesper Velgaard; Mann, Matthias

    2010-01-01

    -translational controls contribute majorly to regulation of protein abundance, for example in heat shock stress response. The development of new sample preparation methods, high-resolution mass spectrometry and novel bioinfomatic tools close this gap and allow the global quantitation of the yeast proteome under different...... conditions. Here, we provide background information on proteomics by mass-spectrometry and describe the practice of a comprehensive yeast proteome analysis....

  20. Subcellular analysis by laser ablation electrospray ionization mass spectrometry

    Science.gov (United States)

    Vertes, Akos; Stolee, Jessica A; Shrestha, Bindesh

    2014-12-02

    In various embodiments, a method of laser ablation electrospray ionization mass spectrometry (LAESI-MS) may generally comprise micro-dissecting a cell comprising at least one of a cell wall and a cell membrane to expose at least one subcellular component therein, ablating the at least one subcellular component by an infrared laser pulse to form an ablation plume, intercepting the ablation plume by an electrospray plume to form ions, and detecting the ions by mass spectrometry.

  1. Chiral recognition detected by fast atom bombardment mass spectrometry.

    Science.gov (United States)

    Sawada, M

    1997-01-01

    Detection of chiral recognition in various intermolecular interaction systems using mass spectrometry has become important for the modern fields of analytical chemistry, organic chemistry, and biochemistry due to the characteristic nature of the rapid method and the trace amount needed. This review presents the various methods for detecting and evaluating chiral recognition used primarily in fast atom bombardment mass spectrometry. Emphasis is put on fundamentals and applications of these methods for variously existing enantioselective intermolecular interaction systems.

  2. X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry characterization of aging effects on the mineral fibers treated with aminopropylsilane and quaternary ammonium compounds

    DEFF Research Database (Denmark)

    Zafar, Ashar; Schjødt-Thomsen, Jan; Sodhi, R.

    2012-01-01

    X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry were used to investigate the aging effects on the aminopropylsilane (APS) and quaternary ammonium surfactant-treated mineral fibers. APS-coated mineral fiber samples were treated with cationic surfactant...... (PCA) was applied to the time-of-flight secondary ion mass spectrometry spectra, and an increase in the intensities of APS characteristic peaks were observed after aging. The observed increase in the signals of APS originates from underlying silanized fibers after the removal of the surfactant...

  3. Calibration using constrained smoothing with applications to mass spectrometry data.

    Science.gov (United States)

    Feng, Xingdong; Sedransk, Nell; Xia, Jessie Q

    2014-06-01

    Linear regressions are commonly used to calibrate the signal measurements in proteomic analysis by mass spectrometry. However, with or without a monotone (e.g., log) transformation, data from such functional proteomic experiments are not necessarily linear or even monotone functions of protein (or peptide) concentration except over a very restricted range. A computationally efficient spline procedure improves upon linear regression. However, mass spectrometry data are not necessarily homoscedastic; more often the variation of measured concentrations increases disproportionately near the boundaries of the instruments measurement capability (dynamic range), that is, the upper and lower limits of quantitation. These calibration difficulties exist with other applications of mass spectrometry as well as with other broad-scale calibrations. Therefore the method proposed here uses a functional data approach to define the calibration curve and also the limits of quantitation under the two assumptions: (i) that the variance is a bounded, convex function of concentration; and (ii) that the calibration curve itself is monotone at least between the limits of quantitation, but not necessarily outside these limits. Within this paradigm, the limit of detection, where the signal is definitely present but not measurable with any accuracy, is also defined. An iterative approach draws on existing smoothing methods to account simultaneously for both restrictions and is shown to achieve the global optimal convergence rate under weak conditions. This approach can also be implemented when convexity is replaced by other (bounded) restrictions. Examples from Addona et al. (2009, Nature Biotechnology 27, 663-641) both motivate and illustrate the effectiveness of this functional data methodology when compared with the simpler linear regressions and spline techniques.

  4. Evaluation and prevention of the negative matrix effect of terpenoids on pesticides in apples quantification by gas chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Giacinti, Géraldine; Raynaud, Christine; Capblancq, Sophie; Simon, Valérie

    2017-02-03

    The sample matrix can enhance the gas chromatography signal of pesticide residues relative to that obtained with the same concentration of pesticide in solvent. This paper is related to negative matrix effects observed in coupled gas chromatography-mass spectrometry ion trap (GC/MS(2)) quantification of pesticides in concentrated extracts of apple peel prepared by the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) method. It is focused on the pesticides most frequently used on the apple varieties studied, throughout the crop cycle, right up to harvest, to combat pests and diseases and to improve fruit storage properties. Extracts from the fleshy receptacle (flesh), the epiderm (peel) and fruit of three apple varieties were studied by high-performance thin-layer chromatography hyphenated with UV-vis light detection (HPTLC/UV visible). The peel extracts had high concentrations of triterpenic acids (oleanolic and ursolic acids), reaching 25mgkg(-1), whereas these compounds were not detected in the flesh extracts (<0.05mgkg(-1)). A significant relationship has been found between the levels of these molecules and negative matrix effects in GC/MS(2). The differences in the behavior of pesticides with respect to matrix effects can be accounted for by the physicochemical characteristics of the molecules (lone pairs, labile hydrogen, conjugation). The HPTLC/UV visible method developed here for the characterization of QuEChERS extracts acts as a complementary clean-up method, aimed to decrease the negative matrix effects of such extracts.

  5. Calcium Isotope Analysis by Mass Spectrometry

    Science.gov (United States)

    Boulyga, S.; Richter, S.

    2010-12-01

    The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. This presentation discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. Additionally, the availability of Ca isotope reference materials will be discussed.

  6. The role of mass spectrometry in atomic weight determinations.

    Science.gov (United States)

    De Laeter, John R

    2009-01-01

    accurate isotopic measurements. Atomic weights can no longer be regarded as constants of nature, except for the monoisotopic elements whose atomic weights are determined solely by the relative atomic mass of that nuclide. Stable isotope geochemists developed mass spectrometric protocols by the adoption of internationally accepted reference materials for the light elements, to which measurements from various laboratories could be compared. Subsequently, a number of heavy elements such as iron, molybdenum and cadmium have been shown to exhibit isotope fractionation. The magnitude of such isotope fractionation in nature is less than for the light elements, but technological developments, such as multiple collector-inductively coupled plasma-mass spectrometry, have enabled such fractionation effects to be determined. Measurements of the atomic weights of certain elements affect the determination of important fundamental constants such as the Avogadro Constant, the Faraday Constant and the Universal Gas Constant. Heroic efforts have been made to refine the accuracy of the atomic weight of silicon, with the objective of replacing the SI standard of mass--the kilogram--with the Avogadro Constant. Improvements in these fundamental constants in turn affect the set of self-consistent values of other basic constants through a least-squares adjustment methodology. Absolute isotope abundances also enable the Solar System abundances of the s-, r-, and p-process of nucleosynthesis to be accurately determined, thus placing constraints on theories of heavy element nucleosynthesis. Future developments in the science of atomic weight determinations are also examined.

  7. Multiresidue analysis of multiclass pesticides and polyaromatic hydrocarbons in fatty fish by gas chromatography tandem mass spectrometry and evaluation of matrix effect.

    Science.gov (United States)

    Chatterjee, Niladri S; Utture, Sagar; Banerjee, Kaushik; Ahammed Shabeer, T P; Kamble, Narayan; Mathew, Suseela; Ashok Kumar, K

    2016-04-01

    This paper reports a selective and sensitive method for multiresidue determination of 119 chemical residues including pesticides and polyaromatic hydrocarbons (PAH) in high fatty fish matrix. The novel sample preparation method involved extraction of the target analytes from homogenized fish meat (5 g) in acetonitrile (15 mL, 1% acetic acid) after three-phase partitioning with hexane (2 mL) and the remaining aqueous layer. An aliquot (1.5 mL) of the acetonitrile layer was aspirated and subjected to two-stage dispersive solid phase extraction (dSPE) cleanup and the residues were finally estimated by gas chromatography mass spectrometry with selected reaction monitoring (GC-MS/MS). The co-eluted matrix components were identified on the basis of their accurate mass by GC with quadrupole time of flight MS. Addition of hexane during extraction and optimized dSPE cleanup significantly minimized the matrix effects. Recoveries at 10, 25 and 50 μg/kg were within 60-120% with associated precision, RSD<11%.

  8. Ortho-hydroxyl effect and proton transfer via ion-neutral complex: the fragmentation study of protonated imine resveratrol analogues in mass spectrometry.

    Science.gov (United States)

    Yue, Lei; Li, Jing; Xie, Xiaodong; Guo, Cheng; Yin, Xinchi; Yin, Qi; Chen, Yinjuan; Pan, Yuanjiang; Ding, Chuanfan

    2016-07-01

    The fragmentation pathways of protonated imine resveratrol analogues in the gas-phase were investigated by electrospray ionization-tandem mass spectrometry. Benzyl cations were formed in the imine resveratrol analogues that had an ortho-hydroxyl group on the benzene ring A. The specific elimination of the quinomethane neutral, CH2  = C6 H4  = O, from the two isomeric ions [M1 + H](+) and [M3 + H](+) via the corresponding ion-neutral complexes was observed. The fragmentation pathway for the related meta-isomer, ion [M2 + H](+) and the other congeners was not observed. Accurate mass measurements and additional experiments carried out with a chlorinated analogue and the trideuterated isotopolog of M1 supported the overall interpretation of the fragmentation phenomena observed. It is very helpful for understanding the intriguing roles of ortho-hydroxyl effect and ion-neutral complexes in fragmentation reactions and enriching the knowledge of the gas-phase chemistry of the benzyl cation. Copyright © 2016 John Wiley & Sons, Ltd.

  9. Calcium isotope analysis by mass spectrometry.

    Science.gov (United States)

    Boulyga, Sergei F

    2010-01-01

    The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. The present article discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. In Sections 2 and 3, mass spectrometric methods applied to precise stable isotope analysis and to the determination of (41)Ca are described. Section 4 contains a short summary of selected applications, and includes tracer experiments and the potential use

  10. [Characterization of matrix effects in microanalysis of sulfide minerals by laser ablation-inductively coupled plasma-mass spectrometry based on an element pair method].

    Science.gov (United States)

    Yuan, Ji-hai; Zhan, Xiu-chun; Hu, Ming-yue; Zhao, Ling-hao; Sun, Dong-yang

    2015-02-01

    Matrix effect between reference materials and samples is one of the major factors affecting the accuracy of analytical results by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). However, there is no method or calculation formula to quantify matrix effect between standards and samples up to date. In this paper, the linear correlation coefficient r of the Ii/I(is-Ci)/Cis graphs of element pairs were used to characterize the matrix effect, which took the ratios of concentrations (ci/ c(is)) and intensities (Ii/Iis) of the analytical element and internal standard element as x-axis and gamma-axis, respectively. Matrix effects of 6 element pairs in 13 glass reference materials, 2 sulfide reference materials and 2 sulfide minerals using Fe as internal standard was studied, with the linear correlation coefficient r of Fe-Cu, Fe-Zn element pairs both less than 0. 999 and trace Fe--Mn, Fe--Co, Fe--Ga, Fe--Pb element pairs all better than 0.999. Matrix effects of 3 major element pairs in 2 sulfide ref- erence materials and 6 sulfide minerals using S as internal standard was also studied, with the linear correlation coefficient r of S--Fe, S--Cu, S--Zn all less than 0.999. The great majority of relative errors of EMPA analytical results for major elements in sulfide minerals were greater than 10%, whether analyzed using Fe as internal standard with glass reference materials as external standard, or S as internal standard with sulfide reference materials MASS-1, IMER-1 as external standard, respectively. But the most analytical results for trace elements calibrated by glass reference materials using Fe as internal standard were well agreed with sulfide standard MASS-1, with the relative errors less than 15%. The results showed that matrix effects existed in glass reference materials, sulfide reference materials and sulfide minerals, and it also proved a certain rationality and practicability for quantification of matrix effect using the linear

  11. Effective elimination of organic matter interference in boron isotopic analysis by thermal ionization mass spectrometry of coral/foraminifera: micro-sublimation technology combined with ion exchange.

    Science.gov (United States)

    He, Maoyong; Xiao, Yingkai; Ma, Yunqi; Jin, Zhangdong; Xiao, Jun

    2011-03-30

    In order to better estimate the effectiveness of micro-sublimation technology on the elimination of organic matter interference during boron isotopic analysis, a series of improved experiments was carried out using simple apparatus. Recovery rates after micro-sublimation were measured for boric acid solutions with different B contents or different B/organic matter ratios. The improved micro-sublimation procedure combined with ion-exchange technology was then used to test natural samples (coral and foraminifera) for the separation of boron. Our results show that the time taken for 100% recovery of different amounts of B differed and that the proportions of B/organic matter within the natural organic matter have little effect on the relationship between the recovery rates of B and the micro-sublimation times. The experiments further confirm that the organic matter does indeed have an effect on boron isotope analyses by positive thermal ionization mass spectrometry and that the use of micro-sublimation can effectively remove interferences from the organic matter during boron isotopic analysis.

  12. Correlating excipient effects on conformational and storage stability of an IgG1 monoclonal antibody with local dynamics as measured by hydrogen/deuterium-exchange mass spectrometry.

    Science.gov (United States)

    Manikwar, Prakash; Majumdar, Ranajoy; Hickey, John M; Thakkar, Santosh V; Samra, Hardeep S; Sathish, Hasige A; Bishop, Steven M; Middaugh, C Russell; Weis, David D; Volkin, David B

    2013-07-01

    The effects of sucrose and arginine on the conformational and storage stability of an IgG1 monoclonal antibody (mAb) were monitored by differential scanning calorimetry (DSC) and size-exclusion chromatography (SEC), respectively. Excipient effects on protein physical stability were then compared with their effects on the local flexibility of the mAb in solution at pH 6, 25°C using hydrogen/deuterium-exchange mass spectrometry (H/D-MS). Compared with a 0.1 M NaCl control, sucrose (0.5 M) increased conformational stability (T(m) values), slowed the rate of monomer loss, reduced the formation of insoluble aggregates, and resulted in a global trend of small decreases in local flexibility across most regions of the mAb. In contrast, the addition of arginine (0.5 M) decreased the mAb's conformational stability, increased the rate of loss of monomer with elevated levels of soluble and insoluble aggregates, and led to significant increases in the local flexibility in specific regions of the mAb, most notably within the constant domain 2 of the heavy chain (C(H)2). These results provide new insights into the effect of sucrose and arginine on the local dynamics of IgG1 domains as well as preliminary correlations between local flexibility within specific segments of the C(H)2 domain (notably heavy chain 241-251) and the mAb's overall physical stability.

  13. Secondary Ion Mass Spectrometry Imaging of Dictyostelium discoideum Aggregation Streams

    Energy Technology Data Exchange (ETDEWEB)

    Debord, J. Daniel; Smith, Donald F.; Anderton, Christopher R.; Heeren, Ronald M.; Pasa-Tolic, Ljiljana; Gomer, Richard H.; Fernandez-Lima, Francisco A.

    2014-06-09

    High resolution imaging mass spectrometry could become a valuable tool for cell and developmental biology, but both, high spatial and mass spectral resolution are needed to enable this. In this report, we employed Bi3 bombardment time-of-flight (Bi3 ToF-SIMS) and C60 bombardment Fourier transform ion cyclotron resonance secondary ion mass spectrometry (C60 FTICR-SIMS) to image Dictyostelium discoideum aggregation streams. Nearly 300 lipid species were identified from the aggregation streams. High resolution mass spectrometry imaging (FTICR-SIMS) enabled the generation of multiple molecular ion maps at the nominal mass level and provided good coverage for fatty acyls, prenol lipids, and sterol lipids. The comparison of Bi3 ToF-SIMS and C60 FTICR-SIMS suggested that while the first provides fast, high spatial resolution molecular ion images, the chemical complexity of biological samples warrants the use of high resolution analyzers for accurate ion identification.

  14. NCBI Peptidome: a new repository for mass spectrometry proteomics data.

    Science.gov (United States)

    Ji, Li; Barrett, Tanya; Ayanbule, Oluwabukunmi; Troup, Dennis B; Rudnev, Dmitry; Muertter, Rolf N; Tomashevsky, Maxim; Soboleva, Alexandra; Slotta, Douglas J

    2010-01-01

    Peptidome is a public repository that archives and freely distributes tandem mass spectrometry peptide and protein identification data generated by the scientific community. Data from all stages of a mass spectrometry experiment are captured, including original mass spectra files, experimental metadata and conclusion-level results. The submission process is facilitated through acceptance of data in commonly used open formats, and all submissions undergo syntactic validation and curation in an effort to uphold data integrity and quality. Peptidome is not restricted to specific organisms, instruments or experiment types; data from any tandem mass spectrometry experiment from any species are accepted. In addition to data storage, web-based interfaces are available to help users query, browse and explore individual peptides, proteins or entire Samples and Studies. Results are integrated and linked with other NCBI resources to ensure dissemination of the information beyond the mass spectroscopy proteomics community. Peptidome is freely accessible at http://www.ncbi.nlm.nih.gov/peptidome.

  15. Proteomics and Mass Spectrometry for Cancer Biomarker Discovery

    Directory of Open Access Journals (Sweden)

    Ming Lu

    2007-01-01

    Full Text Available Proteomics is a rapidly advancing field not only in the field of biology but also in translational cancer research. In recent years, mass spectrometry and associated technologies have been explored to identify proteins or a set of proteins specific to a given disease, for the purpose of disease detection and diagnosis. Such biomarkers are being investigated in samples including cells, tissues, serum/plasma, and other types of body fluids. When sufficiently refined, proteomic technologies may pave the way for early detection of cancer or individualized therapy for cancer. Mass spectrometry approaches coupled with bioinformatic tools are being developed for biomarker discovery and validation. Understanding basic concepts and application of such technology by investigators in the field may accelerate the clinical application of protein biomarkers in disease management.Abbreviations: 2DE: two-dimensional gel electrophoresis; ABPP: activity-based protein profiling; CEA: carcinoembryonic antigen; CI: confidence interval; ESI: electrospray ionization; FP: fluorophosphonate; HPLC: high performance liquid chromatography; ICAT: isotope coded affi nitytags; IEF: isoelectric focusing; iTRAQ: isobaric tags for relative and absolute quantification; LCMS: combined liquid chromatography-mass spectrometry; LCMSMS: liquid chromatography tandem mass spectrometry; LOD: limit of detection; m/z: mass to charge ratio; MALDI: matrix-assisted laser desorption ionization; MS: mass spectrometry; MUDPIT: multidimensional protein identification technology; NAF: nipple aspirate fluid; PMF: peptide mass fingerprinting; PSA: prostate specifi c antigen; PTMs: post-translational modifications; RPMA: reverse phase protein microarray; SELDI: surface enhanced laser desorption ionization; TOF: time-of-flight.

  16. 'Extreme mass spectrometry': the role of mass spectrometry in the study of the Antarctic environment.

    Science.gov (United States)

    Magi, Emanuele; Tanwar, Shivani

    2014-11-01

    A focus on the studies of the Antarctic environment that have been performed by mass spectrometry is presented herein; our aim is to give evidence of the essential role of this instrumental technique in the framework of the scientific research in Antarctica, with a comprehensive review on the main literature of the last two decades. Due to the wideness of the topic, the present review is limited to the determination of organic pollutants, natural molecules and biomarkers in Antarctica, thus excluding elemental analysis and studies on inorganic species. The work has been divided into five sections, on the basis of the considered environmental compartment: air; ice and snow; seawater, pack ice and lakes; soil and sediments; and organisms and biomarkers.

  17. Noncovalent Shiga-like toxin assemblies: characterization by means of mass spectrometry and tandem mass spectrometry.

    Science.gov (United States)

    Williams, Jonathan P; Green, Brian N; Smith, Daniel C; Jennings, Keith R; Moore, Katherine A H; Slade, Susan E; Roberts, Lynne M; Scrivens, James H

    2005-06-14

    Shiga-like toxin 1 (SLTx), produced by enterohemorrhagic strains of Escherichia coli (EHEC), belongs to a family of structurally and functionally related AB(5) protein toxins that are associated with human disease. EHEC infection often gives rise to hemolytic colitis, while toxin-induced kidney damage is one of the major causes of hemolytic uremic syndrome (HUS) and acute renal failure in children. As such, an understanding and analysis of the noncovalent interactions that maintain the quaternary structure of this toxin are fundamentally important since such interactions have significant biochemical and medical implications. This paper reports on the analysis of the noncovalent homopentameric complex of Shiga-like toxin B chain (SLTx-B(5)) using electrospray ionization (ESI) triple-quadrupole (QqQ) mass spectrometry (MS) and tandem mass spectrometry (MS/MS) and the analysis of the noncovalent hexameric holotoxin (SLTx-AB(5)) using ESI time-of-flight (TOF) MS. The triple-quadrupole analysis revealed highly charged monomer ions dissociate from the multiprotein complex to form dimer, trimer, and tetramer product ions, which were also seen to further dissociate. The ESI-TOFMS analysis of SLTx-AB(5) revealed the complex remained intact and was observed in the gas phase over a range of pHs. Theses findings demonstrate that the gas-phase structure observed for both the holotoxin and the isoloated B chains correlates well with the structures reported to exist in the solution phase for these proteins. Such analysis provides a rapid screening technique for assessing the noncovalent structure of this family of proteins and other structurally related toxins.

  18. EP3 Fundamentals of Protein Sequence Characterization by Mass Spectrometry

    OpenAIRE

    Annan, R. S.; Johnson, R. S.; Papayannopoulos, I. A.

    2007-01-01

    The first section of the tutorial will describe the instrumentation typically used in biological mass spectrometry applications related to protein identification. We focus on the relevant ionization techniques, common mass analyzers, and sample introduction systems. Attention will be given to properties, such as mass accuracy and mass resolution, which are important to protein characterization and database search strategies for protein identification. Practical considerations regarding the se...

  19. Investigation of endogenous blood lipids components that contribute to matrix effects in dried blood spot samples by liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Ismaiel, Omnia A; Jenkins, Rand G; Karnes, H Thomas

    2013-08-01

    Dried blood spot (DBS) sampling coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS) is a rapidly developing approach in the field of biopharmaceutical analysis. DBS sampling enables analysis of small sample volumes with high sensitivity and selectivity while providing a convenient easy to store and ship format. Lipid components that may be extracted during biological sample processing may result in matrix ionization effects and can significantly affect the precision and accuracy of the results. Glycerophosphocholines (GPChos), cholesterols and triacylglycerols (TAG) are the main lipid components that contribute to matrix effects in LC-MS/MS. Various organic solvents such as methanol, acetonitrile, methyl tertiary butyl ether, ethyl ether, dichloromethane and n-hexane were investigated for elution of these lipid components from DBS samples. Methanol extracts demonstrated the highest levels of GPChos whereas ethyl ether and n-hexane extracts contained less than 1.0 % of the GPChos levels in the methanol extracts. Ethyl ether extracts contained the highest levels of cholesterols and TAG in comparison to other investigated organic solvents. Acetonitrile is recommended as an elution solvent due to low lipid recoveries. Matrix effects resulted from different extracted lipid components should be studied and assessed carefully in DBS samples.

  20. Use of Tritium Accelerator Mass Spectrometry for Tree Ring Analysis

    Science.gov (United States)

    LOVE, ADAM H.; HUNT, JAMES R.; ROBERTS, MARK L.; SOUTHON, JOHN R.; CHIARAPPA - ZUCCA, MARINA L.; DINGLEY, KAREN H.

    2010-01-01

    Public concerns over the health effects associated with low-level and long-term exposure to tritium released from industrial point sources have generated the demand for better methods to evaluate historical tritium exposure levels for these communities. The cellulose of trees accurately reflects the tritium concentration in the source water and may contain the only historical record of tritium exposure. The tritium activity in the annual rings of a tree was measured using accelerator mass spectrometry to reconstruct historical annual averages of tritium exposure. Milligram-sized samples of the annual tree rings from a Tamarix located at the Nevada Test Site are used for validation of this methodology. The salt cedar was chosen since it had a single source of tritiated water that was well-characterized as it varied over time. The decay-corrected tritium activity of the water in which the salt cedar grew closely agrees with the organically bound tritium activity in its annual rings. This demonstrates that the milligram-sized samples used in tritium accelerator mass spectrometry are suited for reconstructing anthropogenic tritium levels in the environment. PMID:12144257

  1. Pesticide residues screening in wine by mass spectrometry

    Directory of Open Access Journals (Sweden)

    Machado Andrea F.

    2016-01-01

    Full Text Available Recently, a study (from PAN Europe covered 40 bottles of wine – 34 conventional and six organic ones – purchased inside the EU. According to the results, the 34 bottles of conventional wine together contained 148 pesticide residues. All 34 bottles contained from one to ten pesticides, bringing the average per bottle to more than four. Of the six bottles of organic wine tested, one sample contained a low concentration of a possibly carcinogenic pesticide. According to PAN Europe, the “contamination of wines is a direct result of over-reliance on pesticides in grape production”. This study, between others, to prove the importance of develop methods sensivity and confident for pesticide detection in wine. A multi-residue method was developed for the determination ca of 250 pesticide residues in wine using Quechers extraction, gas chromatography-tandem mass spectrometry (GC-MS-MS and liquid chromatography-tandem mass spectrometry (LC-MS-MS. The method was validated with the evaluation of follow parameters: Linearity, Precision, Accuracy, Matrix effect, Limit of detection and Limit of Quantification. The method was approved and was able to quantify pesticide residues in more than 60 samples of wine.

  2. Incorporating Biological Mass Spectrometry into Undergraduate Teaching Labs, Part 2: Peptide Identification via Molecular Mass Determination

    Science.gov (United States)

    Arnquist, Isaac J.; Beussman, Douglas J.

    2009-01-01

    Mass spectrometry has become a routine analytical tool in the undergraduate curriculum in the form of GC-MS. While relatively few undergraduate programs have incorporated biological mass spectrometry into their programs, the importance of these techniques, as demonstrated by their recognition with the 2002 Nobel Prize, will hopefully lead to…

  3. Incorporating Biological Mass Spectrometry into Undergraduate Teaching Labs, Part 2: Peptide Identification via Molecular Mass Determination

    Science.gov (United States)

    Arnquist, Isaac J.; Beussman, Douglas J.

    2009-01-01

    Mass spectrometry has become a routine analytical tool in the undergraduate curriculum in the form of GC-MS. While relatively few undergraduate programs have incorporated biological mass spectrometry into their programs, the importance of these techniques, as demonstrated by their recognition with the 2002 Nobel Prize, will hopefully lead to…

  4. Top-Down Mass Spectrometry: Proteomics to Proteoforms.

    Science.gov (United States)

    Patrie, Steven M

    2016-01-01

    This chapter highlights many of the fundamental concepts and technologies in the field of top-down mass spectrometry (TDMS), and provides numerous examples of contributions that TD is making in biology, biophysics, and clinical investigations. TD workflows include variegated steps that may include non-specific or targeted preparative strategies, orthogonal liquid chromatography techniques, analyte ionization, mass analysis, tandem mass spectrometry (MS/MS) and informatics procedures. This diversity of experimental designs has evolved to manage the large dynamic range of protein expression and diverse physiochemical properties of proteins in proteome investigations, tackle proteoform microheterogeneity, as well as determine structure and composition of gas-phase proteins and protein assemblies.

  5. A Metabolomic Approach to Clarifying the Effect of AST-120 on 5/6 Nephrectomized Rats by Capillary Electrophoresis with Mass Spectrometry (CE-MS

    Directory of Open Access Journals (Sweden)

    Takaaki Abe

    2012-11-01

    Full Text Available The oral adsorbent AST-120 is composed of spherical carbon particles and has an adsorption ability for certain small-molecular-weight compounds that accumulate in patients with chronic kidney disease (CKD. So far, very few compounds are known to be adsorbed by AST-120 in vivo. To examine the effect of AST-120 in vivo, we comprehensively evaluated the plasma concentrations of 146 compounds (61 anions and 85 cations in CKD model rats, with or without four weeks of treatment with AST-120. By capillary electrophoresis with mass spectrometry, we identified 6 anions and 17 cations that were significantly decreased by AST-120 treatment. In contrast, we also identified 2 cations that were significantly increased by AST-120. Among them, 4 anions, apart from indoxyl sulfate and hippurate, and 19 cations were newly identified in this study. The plasma levels of N-acetyl-neuraminate, 4-pyridoxate, 4-oxopentanoate, glycine, γ-guanidinobutyrate, N-γ-ethylglutamine, allantoin, cytosine, 5-methylcytosine and imidazole-4-acetate were significantly increased in the CKD model compared with the sham-operated group, and were significantly decreased by AST-120 treatment. Therefore, these 10 compounds could be added as uremic compounds that indicate the effect of AST-120 treatment. This study provides useful information not only for identifying the indicators of AST-120, but also for clarifying changes in the metabolic profile by AST-120 treatment in the clinical setting.

  6. A metabolomic approach to clarifying the effect of AST-120 on 5/6 nephrectomized rats by capillary electrophoresis with mass spectrometry (CE-MS).

    Science.gov (United States)

    Akiyama, Yasutoshi; Takeuchi, Yoichi; Kikuchi, Koichi; Mishima, Eikan; Yamamoto, Yasuaki; Suzuki, Chitose; Toyohara, Takafumi; Suzuki, Takehiro; Hozawa, Atsushi; Ito, Sadayoshi; Soga, Tomoyoshi; Abe, Takaaki

    2012-11-14

    The oral adsorbent AST-120 is composed of spherical carbon particles and has an adsorption ability for certain small-molecular-weight compounds that accumulate in patients with chronic kidney disease (CKD). So far, very few compounds are known to be adsorbed by AST-120 in vivo. To examine the effect of AST-120 in vivo, we comprehensively evaluated the plasma concentrations of 146 compounds (61 anions and 85 cations) in CKD model rats, with or without four weeks of treatment with AST-120. By capillary electrophoresis with mass spectrometry, we identified 6 anions and 17 cations that were significantly decreased by AST-120 treatment. In contrast, we also identified 2 cations that were significantly increased by AST-120. Among them, 4 anions, apart from indoxyl sulfate and hippurate, and 19 cations were newly identified in this study. The plasma levels of N-acetyl-neuraminate, 4-pyridoxate, 4-oxopentanoate, glycine, γ-guanidinobutyrate, N-γ-ethylglutamine, allantoin, cytosine, 5-methylcytosine and imidazole-4-acetate were significantly increased in the CKD model compared with the sham-operated group, and were significantly decreased by AST-120 treatment. Therefore, these 10 compounds could be added as uremic compounds that indicate the effect of AST-120 treatment. This study provides useful information not only for identifying the indicators of AST-120, but also for clarifying changes in the metabolic profile by AST-120 treatment in the clinical setting.

  7. NEGATIVE-ION MASS SPECTROMETRY OF SULFONYLUREA HERBICIDES

    Science.gov (United States)

    Sulfonylurea herbicides have been studied using neg-ion desorption chem.-ionization (DCI) mass spectrometry (MS) and DCI-MS/MS techniques. Both {M-H]- and M.- ions were obsd. in the DCI mass spectra. The collisonally activated dissocn. (CAD) spectra were characteristic of the str...

  8. A Review of the Emerging Field of Underwater Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Emily Chua

    2016-11-01

    Full Text Available Mass spectrometers are versatile sensor systems, owing to their high sensitivity and ability to simultaneously measure multiple chemical species. Over the last two decades, traditional laboratory-based membrane inlet mass spectrometers have been adapted for underwater use. Underwater mass spectrometry has drastically improved our capability to monitor a broad suite of gaseous compounds (e.g., dissolved atmospheric gases, light hydrocarbons, and volatile organic compounds in the aquatic environment. Here we provide an overview of the progress made in the field of underwater mass spectrometry since its inception in the 1990s to the present. In particular, we discuss the approaches undertaken by various research groups in developing in situ mass spectrometers. We also provide examples to illustrate how underwater mass spectrometers have been used in the field. Finally, we present future trends in the field of in situ mass spectrometry. Most of these efforts are aimed at improving the quality and spatial and temporal scales of chemical measurements in the ocean. By providing up-to-date information on underwater mass spectrometry, this review offers guidance for researchers interested in adapting this technology as well as goals for future progress in the field.

  9. Surface-MALDI mass spectrometry in biomaterials research

    DEFF Research Database (Denmark)

    Griesser, H.J.; Kingshott, P.; McArthur, S.L.;

    2004-01-01

    Matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) has been used for over a decade for the determination of purity and accurate molecular masses of macromolecular analytes, such as proteins, in solution. In the last few years the technique has been adapted to become a new...

  10. Applications of Mass Spectrometry to Structural Analysis of Marine Oligosaccharides

    Directory of Open Access Journals (Sweden)

    Yinzhi Lang

    2014-06-01

    Full Text Available Marine oligosaccharides have attracted increasing attention recently in developing potential drugs and biomaterials for their particular physical and chemical properties. However, the composition and sequence analysis of marine oligosaccharides are very challenging for their structural complexity and heterogeneity. Mass spectrometry (MS has become an important technique for carbohydrate analysis by providing more detailed structural information, including molecular mass, sugar constituent, sequence, inter-residue linkage position and substitution pattern. This paper provides an overview of the structural analysis based on MS approaches in marine oligosaccharides, which are derived from some biologically important marine polysaccharides, including agaran, carrageenan, alginate, sulfated fucan, chitosan, glycosaminoglycan (GAG and GAG-like polysaccharides. Applications of electrospray ionization mass spectrometry (ESI-MS are mainly presented and the general applications of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS are also outlined. Some technical challenges in the structural analysis of marine oligosaccharides by MS have also been pointed out.

  11. Applications of mass spectrometry to structural analysis of marine oligosaccharides.

    Science.gov (United States)

    Lang, Yinzhi; Zhao, Xia; Liu, Lili; Yu, Guangli

    2014-06-30

    Marine oligosaccharides have attracted increasing attention recently in developing potential drugs and biomaterials for their particular physical and chemical properties. However, the composition and sequence analysis of marine oligosaccharides are very challenging for their structural complexity and heterogeneity. Mass spectrometry (MS) has become an important technique for carbohydrate analysis by providing more detailed structural information, including molecular mass, sugar constituent, sequence, inter-residue linkage position and substitution pattern. This paper provides an overview of the structural analysis based on MS approaches in marine oligosaccharides, which are derived from some biologically important marine polysaccharides, including agaran, carrageenan, alginate, sulfated fucan, chitosan, glycosaminoglycan (GAG) and GAG-like polysaccharides. Applications of electrospray ionization mass spectrometry (ESI-MS) are mainly presented and the general applications of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) are also outlined. Some technical challenges in the structural analysis of marine oligosaccharides by MS have also been pointed out.

  12. Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS: A New Tool for the Analysis of Toxicological Effects on Single Cell Level

    Directory of Open Access Journals (Sweden)

    Harald Jungnickel

    2016-02-01

    Full Text Available Single cell imaging mass spectrometry opens up a complete new perspective for strategies in toxicological risk assessment and drug discovery. In particular, time-of-flight secondary ion mass spectrometry (ToF-SIMS with its high spatial and depth resolution is becoming part of the imaging mass spectrometry toolbox used for single cell analysis. Recent instrumentation advancements in combination with newly developed cluster ion guns allow 3-dimensional reconstruction of single cells together with a spatially resolved compound location and quantification on nanoscale depth level. The exact location and quantification of a single compound or even of a set of compounds is no longer restricted to the two dimensional space within single cells, but is available for voxels, a cube-sized 3-dimensional space, rather than pixels. The information gathered from one voxel is further analysed using multivariate statistical methodology like maximum autocorrelation factors to co-locate the compounds of interest within intracellular organelles like nucleus, mitochondria or golgi apparatus. Furthermore, the cell membrane may be resolved, including adhering compounds and potential changes of the lipid patterns. The generated information can be used further for a first evaluation of intracellular target specifity of new drug candidates or for the toxicological risk assessment of environmental chemicals and their intracellular metabolites. Additionally, single cell lipidomics and metabolomics enable for the first time an in-depth understanding of the activation or inhibition of cellular biosynthesis and signalling pathways.

  13. An effective method of UV-oxidation of dissolved organic carbon in natural waters for radiocarbon analysis by accelerator mass spectrometry

    Science.gov (United States)

    Xue, Yuejun; Ge, Tiantian; Wang, Xuchen

    2015-12-01

    Radiocarbon (14C) measurement of dissolved organic carbon (DOC) is a very powerful tool to study the sources, transformation and cycling of carbon in the ocean. The technique, however, remains great challenges for complete and successful oxidation of sufficient DOC with low blanks for high precision carbon isotopic ratio analysis, largely due to the overwhelming proportion of salts and low DOC concentrations in the ocean. In this paper, we report an effective UV-Oxidation method for oxidizing DOC in natural waters for radiocarbon analysis by accelerator mass spectrometry (AMS). The UV-oxidation system and method show 95%±4% oxidation efficiency and high reproducibility for DOC in both river and seawater samples. The blanks associated with the method was also low (about 3 µg C) that is critical for 14C analysis. As a great advantage of the method, multiple water samples can be oxidized at the same time so it reduces the sample processing time substantially compared with other UV-oxidation method currently being used in other laboratories. We have used the system and method for 14C studies of DOC in rivers, estuaries, and oceanic environments and have received promise results.

  14. Effect of the systemic versus inhalatory administration of synthetic glucocorticoids on the urinary steroid profile as studied by gas chromatography-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Mazzarino, Monica [Laboratorio Antidoping, Federazione Medico Sportiva Italiana, Largo Giulio Onesti 1, 00197 Rome (Italy); Rossi, Francesca [Laboratorio Antidoping, Federazione Medico Sportiva Italiana, Largo Giulio Onesti 1, 00197 Rome (Italy); Giacomelli, Laura [Dipartimento di Scienze Chirurgiche, Universita La Sapienza, Viale Regina Elena 324, 00161 Rome (Italy); Botre, Francesco [Laboratorio Antidoping, Federazione Medico Sportiva Italiana, Largo Giulio Onesti 1, 00197 Rome (Italy) and Dipartimento CGMIA, Universita La Sapienza, Via del Castro Laurenziano 9, 00161 Rome (Italy)]. E-mail: francesco.botre@uniroma1.it

    2006-02-10

    This paper presents a gas chromatography-mass spectrometry (GC-MS) study carried out on human urine to verify whether the administration of glucocorticoids can affect the urinary steroid profile, and especially the levels of endogenous glucocorticoids, androgens and their main metabolites. Betamethasone and beclomethasone, administered either systemically (per os or i.m.) or locally (by inhalation) have been studied. The determination of the urinary levels of endogenous glucocorticoids and androgens was carried out by GC-MS in electron impact ionization mode. Data were evaluated taking into account the baseline individual variability, and compared with values obtained on a control group. Detectable differences were recorded in the steroids metabolites excretion profiles between men and women. The circadian variability of the steroid profile was the same for both sexes, showing a maximum during the morning hours. After systemic treatment with synthetic glucocorticoids, the relative urinary concentrations of corticosteroids, androgens and of their metabolites were significantly altered, recording a transient decrease of the concentration of cortisol and tetrahydrocortisol and a parallel, although less pronounced, increase of the concentration of testosterone, epitestosterone and related androgenic steroids; while no effects were recorded if the administration was by inhalation.

  15. Effect of six Chinese spices on heterocyclic amine profiles in roast beef patties by ultra performance liquid chromatography-tandem mass spectrometry and principal component analysis.

    Science.gov (United States)

    Zeng, Maomao; He, Zhiyong; Zheng, Zongping; Qin, Fang; Tao, Guanjun; Zhang, Shuang; Gao, Yahui; Chen, Jie

    2014-10-01

    The effects of Chinese spices on the profiles of 17 heterocyclic amines (HAs) from seven HA categories were investigated in roast beef patties using Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry (UPLC-MS/MS) and principal component analysis. Three groups of HAs, imidazopyridines (PhIP, DMIP, and 1,5,6-TMIP), imidazoquinoxalines (MeIQx and 4,8-DiMeIQx), and β-carbolines (harman and norharman), were detected and quantified in all of the samples. The results demonstrated that the total HA and imidazopyridine profiles could clearly be affected by 1% pricklyash peel (14.1 ± 0.76 and 6.06 ± 0.32 ng/g), chilli (41.0 ± 0.01 and 23.0 ± 0.52 ng/g), and cumin (59.9 ± 2.44 and 31.1 ± 3.06 ng/g), in comparison with control values of 21.8 ± 2.40 and 14.3 ± 2.04 ng/g, respectively. The difference was only significant (p spices in meat processing to minimize HA formation.

  16. Simultaneous determination of 13 phytohormones in oilseed rape tissues by liquid chromatography-electrospray tandem mass spectrometry and the evaluation of the matrix effect.

    Science.gov (United States)

    Fan, Sufang; Wang, Xiupin; Li, Peiwu; Zhang, Qi; Zhang, Wen

    2011-03-01

    In the experiment, a high-performance liquid chromatography and electrospray ionization-tandem mass spectrometry with selected reaction monitoring was used to simultaneously determine various classes of phytohormones, including indole-3-acetic acid, α-naphthaleneacetic acid, 2-chlorobenzoic acid, 4-chlorobenzoic acid, indole-3-butyric acid, gibberellic acid, 2,4-dichlorophenoxyacetic acid, 2-naphthoxyacetic acid, abscisic acid, 2,3,5-triiodobenzoic acid, uniconazole, paclobutrazol and 2,4-epibassinolide in rape tissues. The analyses were separated by an HPLC equipped with a reversed-phase column using a binary solvent system composed of methanol and water, both containing 0.1% of formic acid. The matrix effect was also considered and determined. The technology was applied to analyze rape tissues, including roots, stems, leaves, flowers, immature pods and rape seeds. The rape tissues were subjected to ultrasound-assisted extraction and purified by dispersive solid-phase extraction, and then transferred into the liquid chromatography system. The detection limit for each plant hormone was defined by the ratio of signal/background noise (S/N) of 3. The results showed perfect linearity (R(2) values of 0.9987-1.0000) and reproducibility of elution times (relative standard deviations, RSDs,<1%) and peak areas (RSDs,<7%) for all target compounds.

  17. Validation and assessment of matrix effect and uncertainty of a gas chromatography coupled to mass spectrometry method for pesticides in papaya and avocado samples

    Directory of Open Access Journals (Sweden)

    Norma Susana Pano-Farias

    2017-07-01

    Full Text Available In this paper a method of using the “quick, easy, cheap, effective, rugged, and safe” (QuEChERS extraction and gas chromatography coupled to mass spectrometry detection (GC–MS was developed for the analysis of five frequently applied pesticides in papaya and avocado. The selected pesticides, ametryn, atrazine, carbaryl, carbofuran, and methyl parathion, represent the most commonly used classes (carbamates, organophosphorous, and triazines. Optimum separation achieved the analysis of all pesticides in 0.99. The limits of detection (LOD and quantification (LOQ in papaya ranged from 0.03 mg/kg to 0.35 mg/kg and from 0.06 mg/kg to 0.75 mg/kg, respectively. Meanwhile for avocado, LOD values varied from 0.14 mg/kg to 0.28 mg/kg and LOQ values ranged from 0.22 mg/kg to 0.40 mg/kg. Recoveries obtained for each pesticide in both matrices ranged between 60.6% and 104.3%. The expanded uncertainty of the method was < 26% for all the pesticides in both fruits. Finally, the method was applied to other fruits.

  18. Development of stereotactic mass spectrometry for brain tumor surgery.

    Science.gov (United States)

    Agar, Nathalie Y R; Golby, Alexandra J; Ligon, Keith L; Norton, Isaiah; Mohan, Vandana; Wiseman, Justin M; Tannenbaum, Allen; Jolesz, Ferenc A

    2011-02-01

    Surgery remains the first and most important treatment modality for the majority of solid tumors. Across a range of brain tumor types and grades, postoperative residual tumor has a great impact on prognosis. The principal challenge and objective of neurosurgical intervention is therefore to maximize tumor resection while minimizing the potential for neurological deficit by preserving critical tissue. To introduce the integration of desorption electrospray ionization mass spectrometry into surgery for in vivo molecular tissue characterization and intraoperative definition of tumor boundaries without systemic injection of contrast agents. Using a frameless stereotactic sampling approach and by integrating a 3-dimensional navigation system with an ultrasonic surgical probe, we obtained image-registered surgical specimens. The samples were analyzed with ambient desorption/ionization mass spectrometry and validated against standard histopathology. This new approach will enable neurosurgeons to detect tumor infiltration of the normal brain intraoperatively with mass spectrometry and to obtain spatially resolved molecular tissue characterization without any exogenous agent and with high sensitivity and specificity. Proof of concept is presented in using mass spectrometry intraoperatively for real-time measurement of molecular structure and using that tissue characterization method to detect tumor boundaries. Multiple sampling sites within the tumor mass were defined for a patient with a recurrent left frontal oligodendroglioma, World Health Organization grade II with chromosome 1p/19q codeletion, and mass spectrometry data indicated a correlation between lipid constitution and tumor cell prevalence. The mass spectrometry measurements reflect a complex molecular structure and are integrated with frameless stereotaxy and imaging, providing 3-dimensional molecular imaging without systemic injection of any agents, which can be implemented for surgical margins delineation of

  19. Hydrophilic interaction chromatography versus reversed phase liquid chromatography coupled to mass spectrometry: effect of electrospray ionization source geometry on sensitivity.

    Science.gov (United States)

    Periat, Aurélie; Kohler, Isabelle; Bugey, Aurélie; Bieri, Stefan; Versace, François; Staub, Christian; Guillarme, Davy

    2014-08-22

    In this study, the influence of electrospray ionization (ESI) source design on the overall sensitivity achieved in hydrophilic interaction chromatography (HILIC) and reversed phase liquid chromatography (RPLC), was investigated. State-of-the-art triple quadrupole mass analyzers from AB Sciex, Agilent Technologies and Waters equipped with brand specific source geometries were tested with various mobile phase pH on 53 pharmaceutical compounds. The design of the ESI source showed to strongly influence the gain in sensitivity that can be achieved in HILIC compared to RPLC mode. The 6460 Triple Quadrupole LC/MS system from Agilent Technologies was particularly affected by mobile phase settings. Indeed, compared to RPLC conditions, 92% of the compounds had an increased signal-to-noise ratio at a flow rate of 300 μL/min in HILIC mode at pH 6, while this percentage dropped to only 7% at 1000 μL/min and pH 3. In contrast, the influence of flow rate and mobile phase pH on the gain in sensitivity between RPLC and HILIC was found very limited with the API 5000 LC/MS/MS system from AB Sciex, as only 15 to 36% of the tested compounds showed an enhanced sensitivity in HILIC mode. With the Xevo TQ-S instrument from Waters, superior sensitivity in HILIC was noticed for 85% of the compounds with optimal conditions (i.e., pH 3 and 1000 μL/min), whereas at sub-optimal conditions (i.e. pH 6 and 300 μL/min), it represented less than 50%. The gain in sensitivity observed in HILIC was found less significant with the recent LC-MS platforms used in this study than for old-generation instruments. Indeed, the improved ESI sources equipping the recent mass analyzers allow for enhanced evaporation efficiency, mainly for RPLC mobile phases containing high proportion of water and this even at high flow rates. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Development of rapid methodologies for the isolation and quantitation of drug metabolites by differential mobility spectrometry - mass spectrometry.

    Science.gov (United States)

    Hall, Adam B; Coy, Stephen L; Nazarov, Erkinjon; Vouros, Paul

    2012-09-01

    Clinical and forensic toxicology laboratories are inundated with thousands of samples requiring lengthy chromatographic separations prior to mass spectrometry. Here, we employ differential mobility spectrometry (DMS) interfaced to nano-electrospray ionization-mass spectrometry to provide a rapid ion filtration technique for the separation of ions in gas phase media prior to mass spectral analysis on a DMS-integrated AB SCIEX API 3000 triple-quadrupole mass spectrometer. DMS is efficient at the rapid separation of ions under ambient conditions and provides many advantages when used as an ion filtration technique in tandem with mass spectrometry (MS) and MS/MS. Our studies evaluated DMS-MS/MS as a rapid, quantitative platform for the analysis of drug metabolites isolated from urine samples. In targeted applications, five metabolites of common drugs of abuse were effectively and rapidly separated using isopropanol and ethyl acetate as transport gas modifiers, eliminating the gas chromatography or liquid chromatography-based separations commonly employed in clinical and forensic toxicology laboratories. Calibration curves were prepared for the selected drug metabolites utilizing deuterated internal standards for quantitative purposes. The feasibility of separating and quantitating drug metabolites in a rapid fashion was evaluated by compensation voltage stepping followed by multiple reaction monitoring (MRM) detection. Rapid profiling of clinical and forensic toxicology samples could help to address an urgent need within the scientific community by developing high-throughput analytical methodologies, which could reduce significant case backlogs present within these laboratories.

  1. Charge Transfer Dissociation (CTD) Mass Spectrometry of Peptide Cations: Study of Charge State Effects and Side-Chain Losses

    Science.gov (United States)

    Li, Pengfei; Jackson, Glen P.

    2017-01-01

    1+, 2+, and 3+ precursors of substance P and bradykinin were subjected to helium cation irradiation in a 3D ion trap mass spectrometer. Charge exchange with the helium cations produces a variety of fragment ions, the number and type of which are dependent on the charge state of the precursor ions. For 1+ peptide precursors, fragmentation is generally restricted to C-CO backbone bonds (a and x ions), whereas for 2+ and 3+ peptide precursors, all three backbone bonds (C-CO, C-N, and N-Cα) are cleaved. The type of backbone bond cleavage is indicative of possible dissociation channels involved in CTD process, including high-energy, kinetic-based, and ETD-like pathways. In addition to backbone cleavages, amino acid side-chain cleavages are observed in CTD, which are consistent with other high-energy and radical-mediated techniques. The unique dissociation pattern and supplementary information available from side-chain cleavages make CTD a potentially useful activation method for the structural study of gas-phase biomolecules.

  2. Laser electrospray mass spectrometry of adsorbed molecules at atmospheric pressure

    Science.gov (United States)

    Brady, John J.; Judge, Elizabeth J.; Simon, Kuriakose; Levis, Robert J.

    2010-02-01

    Atmospheric pressure mass analysis of solid phase biomolecules is performed using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples at atmospheric pressure for subsequent electrospray ionization and transfer into a mass spectrometer. LEMS was used to detect a complex molecule (irinotecan HCl), a complex mixture (cold medicine formulation with active ingredients: acetaminophen, dextromethorphan HBr and doxylamine succinate), and a biological building block (deoxyguanosine) deposited on steel surfaces without a matrix molecule.

  3. Advanced Mass Calibration and Visualization for FT-ICR Mass Spectrometry Imaging

    CERN Document Server

    Smith, Donald F; Konijnenburg, Marco; Klinkert, Ivo; Pasa-Tolic, Ljiljana; Heeren, Ron M A

    2013-01-01

    Mass spectrometry imaging by Fourier transform ion cyclotron resonance yields hundreds of unique peaks, many of which cannot be resolved by lower performance mass spectrometers. The high mass accuracy and high mass resolving power allow confident identification of small molecules and lipids directly from biological tissue sections. Here, calibration strategies for Fourier transform ion cyclotron resonance mass spectrometry imaging were investigated. Sub parts-per-million mass accuracy is demonstrated over an entire tissue section. Ion abundance fluctuations are corrected for by addition of total and relative ion abundances for a root-mean-square error of 0.158 ppm on 16,764 peaks. A new approach for visualization of Fourier transform ion cyclotron resonance mass spectrometry imaging data at high resolution is presented. The Mosaic Data-cube provides a flexible means to visualize the entire mass range at a mass spectral bin width of 0.001 Dalton. The high resolution Mosaic Data-cube resolves spectral features ...

  4. Structural and surface coverage effects on CO oxidation reaction over carbon-supported Pt nanoparticles studied by quadrupole mass spectrometry and diffuse reflectance FTIR spectroscopy.

    Science.gov (United States)

    Cheah, Seng Kian; Bernardet, Véronique P; Franco, Alejandro A; Lemaire, Olivier; Gelin, Patrick

    2016-06-01

    The CO oxidation reaction on carbon-supported Pt nanoparticles (average size of 2.8 to 7.7 nm) was studied under flowing conditions at atmospheric pressure and temperatures between 300 and 353 K by coupling quadrupole mass spectrometry (QMS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The Pt loading was varied between 20 and 60 wt%. Gases diluted in He (0.5 mol%) were used together with Ar as a tracer. Reactions with CO and O2 introduced separately onto the samples were studied by QMS, applying successive step changes of the reaction mixtures. Variations in the rate of the reactions were observed and correlated with changes of the calculated coverage of the Pt surface by CO and/or O adspecies at varying steps of the experiment. The transient reaction of CO(g) with adsorbed O (Oad) was fast and mass transport-limited while that of O2(g) with adsorbed CO (COad) was sluggish. Following the same experimental procedures, FTIR spectra of adsorbed CO after varying steps were recorded, confirming the variations of COad and Oad as determined by QMS and indicating changes in the CO distribution over varying types of Pt surface sites. The influence of the adlayer composition (co-adsorption of COad and Oad), the particle size/structure and some possible surface reconstruction effects on the CO oxidation rate were evidenced and discussed. The structure of the Pt nanoparticles supported on carbon appears as an important factor for the efficiency of the so-called O2 bleeding as a CO mitigation strategy in polymer electrolyte membrane fuel cells.

  5. Pharmaceutical metabolite profiling using quadrupole/ion mobility spectrometry/time-of-flight mass spectrometry.

    Science.gov (United States)

    Chan, Eric C Y; New, Lee Sun; Yap, Chun Wei; Goh, Lin Tang

    2009-02-01

    The use of hybrid quadrupole ion mobility spectrometry time-of-flight mass spectrometry (Q/IMS/TOFMS) in the metabolite profiling of leflunomide (LEF) and acetaminophen (APAP) is presented. The IMS drift times (T(d)) of the drugs and their metabolites were determined in the IMS/TOFMS experiments and correlated with their exact monoisotopic masses and other in silico generated structural properties, such as connolly molecular area (CMA), connolly solvent-excluded volume (CSEV), principal moments of inertia along the X, Y and Z Cartesian coordinates (MI-X, MI-Y and MI-Z), inverse mobility and collision cross-section (CCS). The correlation of T(d) with these parameters is presented and discussed. IMS/TOF tandem mass spectrometry experiments (MS(2) and MS(3)) were successfully performed on the N-acetyl-p-benzoquinoneimine glutathione (NAPQI-GSH) adduct derived from the in vitro microsomal metabolism of APAP. As comparison, similar experiments were also performed using hybrid triple quadrupole linear ion trap mass spectrometry (QTRAPMS) and quadrupole time-of-flight mass spectrometry (QTOFMS). The abilities to resolve the product ions of the metabolite within the drift tube and fragment the ion mobility resolved product ions in the transfer travelling wave-enabled stacked ring ion guide (TWIG) demonstrated the potential applicability of the Q/IMS/TOFMS technique in pharmaceutical metabolite profiling.

  6. Broad Separation of Isomeric Lipids by High-Resolution Differential Ion Mobility Spectrometry with Tandem Mass Spectrometry

    Science.gov (United States)

    Bowman, Andrew P.; Abzalimov, Rinat R.; Shvartsburg, Alexandre A.

    2017-08-01

    Maturation of metabolomics has brought a deeper appreciation for the importance of isomeric identity of lipids to their biological role, mirroring that for proteoforms in proteomics. However, full characterization of the lipid isomerism has been thwarted by paucity of rapid and effective analytical tools. A novel approach is ion mobility spectrometry (IMS) and particularly differential or field asymmetric waveform IMS (FAIMS) at high electric fields, which is more orthogonal to mass spectrometry. Here we broadly explore the power of FAIMS to separate lipid isomers, and find a 75% success rate across the four major types of glycero- and phospho- lipids ( sn, chain length, double bond position, and cis/ trans). The resolved isomers were identified using standards, and (for the first two types) tandem mass spectrometry. These results demonstrate the general merit of incorporating high-resolution FAIMS into lipidomic analyses.

  7. Measurement of macrocyclic trichothecene in floor dust of water-damaged buildings using gas chromatography/tandem mass spectrometry-dust matrix effects.

    Science.gov (United States)

    Saito, Rena; Park, Ju-Hyeong; LeBouf, Ryan; Green, Brett J; Park, Yeonmi

    2016-01-01

    Gas chromatography-tandem mass spectrometry (GC-MS/MS) was used to detect fungal secondary metabolites. Detection of verrucarol, the hydrolysis product of Stachybotrys chartarum macrocyclic trichothecene (MCT), was confounded by matrix effects associated with heterogeneous indoor environmental samples. In this study, we examined the role of dust matrix effects associated with GC-MS/MS to better quantify verrucarol in dust as a measure of total MCT. The efficiency of the internal standard (ISTD, 1,12-dodecanediol), and application of a matrix-matched standard correction method in measuring MCT in floor dust of water-damaged buildings was additionally examined. Compared to verrucarol, ISTD had substantially higher matrix effects in the dust extracts. The results of the ISTD evaluation showed that without ISTD adjustment, there was a 280% ion enhancement in the dust extracts compared to neat solvent. The recovery of verrucarol was 94% when the matrix-matched standard curve without the ISTD was used. Using traditional calibration curves with ISTD adjustment, none of the 21 dust samples collected from water damaged buildings were detectable. In contrast, when the matrix-matched calibration curves without ISTD adjustment were used, 38% of samples were detectable. The study results suggest that floor dust of water-damaged buildings may contain MCT. However, the measured levels of MCT in dust using the GC-MS/MS method could be significantly under- or overestimated, depending on the matrix effects, the inappropriate ISTD, or combination of the two. Our study further shows that the routine application of matrix-matched calibration may prove useful in obtaining accurate measurements of MCT in dust derived from damp indoor environments, while no isotopically labeled verrucarol is available.

  8. A study of common discovery dosing formulation components and their potential for causing time-dependent matrix effects in high-performance liquid chromatography tandem mass spectrometry assays.

    Science.gov (United States)

    Xu, Xiaoying; Mei, Hong; Wang, Shiyong; Zhou, Qiao; Wang, Ganfeng; Broske, Lisa; Pena, Adrienne; Korfmacher, Walter A

    2005-01-01

    Hydroxyproyl-beta-cyclodextran (HPBCD), methyl cellulose (MC), Tween 80 and PEG400 are commonly used in dosing formulations in pharmacokinetic (PK) studies during the early drug discovery stage. A series of studies was designed to evaluate the potential matrix effects of these dosing vehicles when the samples are assayed by high-performance liquid chromatography combined with tandem mass spectrometry (HPLC/MS/MS). These dosing vehicles were dosed into the rats via either an intravenous (IV) or an oral route (PO) and plasma samples were collected for a 24-h post-dose period. Five test compounds with CLog P values ranging from 0.9 to 5.4 were spiked into the collected rat plasma. After protein precipitation, these samples were analyzed using a generic fast-gradient HPLC/MS/MS method. Three popular mass spectrometers (Thermo-Finnigan Quantum with ESI and APCI, AB-Sciex API 3000 with ESI and APCI, and Waters-Micromass Quattro Ultima with ESI) were used to test these plasma samples. Results indicated that there was no observed matrix effect for all five compounds when 20% HPBCD or 0.4% MC was used as the vehicle in either the IV or the PO route, respectively. In addition, 0.1% Tween 80 dosed either IV or PO caused significant ion suppression (50-80%, compared to results obtained from plasma samples free from vehicles) for compounds that eluted at the beginning of the chromatogram. Also, PEG400 when used in an oral formulation caused significant ion suppression (30-50%) for early eluting compounds. These matrix effects were not only ionization mode (ESI or APCI) dependent, but also source design (Thermo-Finnigan, AB-Sciex or Waters-Micromass) dependent. Overall, the APCI mode proved to be less vulnerable to matrix effects than the ESI mode. Some possible mechanisms of these matrix effects are proposed and simple strategies to avoid these matrix effects are discussed. Copyright (c) 2005 John Wiley & Sons, Ltd.

  9. Effects of Activating Mutations on EGFR Cellular Protein Turnover and Amino Acid Recycling Determined Using SILAC Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Michael J. Greig

    2015-01-01

    Full Text Available Rapid mutations of proteins that are targeted in cancer therapy often lead to drug resistance. Often, the mutation directly affects a drug’s binding site, effectively blocking binding of the drug, but these mutations can have other effects such as changing the protein turnover half-life. Utilizing SILAC MS, we measured the cellular turnover rates of an important non-small cell lung cancer target, epidermal growth factor receptor (EGFR. Wild-type (WT EGFR, EGFR with a single activating mutant (Del 746–750 or L858R, and the drug-resistant double mutant (L858R/T790M EGFR were analyzed. In non-small cell lung cancer cell lines, EGFR turnover rates ranged from 28 hours in A431 cells (WT to 7.5 hours in the PC-9 cells (Del 746–750 mutant. The measurement of EGFR turnover rate in PC-9 cells dosed with irreversible inhibitors has additional complexity due to inhibitor effects on cell viability and results were reported as a range. Finally, essential amino acid recycling (K and R was measured in different cell lines. The recycling was different in each cell line, but the overall inclusion of the effect of amino acid recycling on calculating EGFR turnover rates resulted in a 10–20% reduction in rates.

  10. Sample preparation in biological mass spectrometry

    CERN Document Server

    Ivanov, Alexander R

    2011-01-01

    The aim of this book is to provide the researcher with important sample preparation strategies in a wide variety of analyte molecules, specimens, methods, and biological applications requiring mass spectrometric analysis as a detection end-point.

  11. Issues and opportunities in accelerator mass spectrometry for stable isotopes.

    Science.gov (United States)

    Matteson, Sam

    2008-01-01

    Accelerator mass spectrometry (AMS) has developed in the last 30 years many notable applications to the spectrometry of radioisotopes, particularly in radiocarbon dating. The instrumentation science of trace element AMS (TEAMS) that analyzes stable isotopes, also called Accelerator SIMS or MegaSIMS, while unique in many features, has also shared in many of these significant advances and has pushed TEAMS sensitivity to concentration levels surpassing many competing mass spectroscopic technologies. This review examines recent instrumentation developments, the capabilities of the new instrumentation and discernable trends for future development.

  12. Xenon purity analysis for EXO-200 via mass spectrometry

    CERN Document Server

    Dobi, A; Slutsky, S; Yen, Y -R; Aharmin, B; Auger, M; Barbeau, P S; Benitez-Medina, C; Breidenbach, M; Cleveland, B; Conley, R; Cook, J; Cook, S; Counts, I; Craddock, W; Daniels, T; Davis, C G; Davis, J; deVoe, R; Dixit, M; Dolinski, M J; Donato, K; Fairbank, W; Farine, J; Fierlinger, P; Franco, D; Giroux, G; Gornea, R; Graham, K; Gratta, G; Green, C; Hagemann, C; Hall, K; Hallman, D; Hargrove, C; Herrin, S; Hughes, M; Hodgson, J; Juget, F; Karelin, A; Kaufman, L J; Kuchenkov, A; Kumar, K; Leonard, D S; Lutter, G; Mackay, D; MacLellan, R; Marino, M; Mong, B; Díez, M Montero; Morgan, P; Müller, A R; Neilson, R; Odian, A; O'Sullivan, K; Piepke, A; Pocar, A; Prescott, C Y; Pushkin, K; Rivas, A; Rollin, E; Rowson, P C; Sabourov, A; Sinclair, D; Skarpaas, K; Stekhanov, V; Strickland, V; Swift, M; Twelker, K; Vuilleumier, J -L; Vuilleumier, J -M; Weber, M; Wichoski, U; Wodin, J; Wright, J D; Yang, L

    2011-01-01

    We describe purity measurements of the natural and enriched xenon stockpiles used by the EXO-200 double beta decay experiment based on a mass spectrometry technique. The sensitivity of the spectrometer is enhanced by several orders of magnitude by the presence of a liquid nitrogen cold trap, and many impurity species of interest can be detected at the level of one part-per-billion or better. We have used the technique to screen the EXO-200 xenon before, during, and after its use in our detector, and these measurements have proven useful. This is the first application of the cold trap mass spectrometry technique to an operating physics experiment.

  13. Direct Protocol for Ambient Mass Spectrometry Imaging on Agar Culture.

    Science.gov (United States)

    Angolini, Célio Fernando F; Vendramini, Pedro Henrique; Araújo, Francisca D S; Araújo, Welington L; Augusti, Rodinei; Eberlin, Marcos N; de Oliveira, Luciana Gonzaga

    2015-07-07

    Herein we describe a new protocol that allows direct mass spectrometry imaging (IMS) of agar cultures. A simple sample dehydration leads to a thin solid agar, which enables the direct use of spray-based ambient mass spectrometry techniques. To demonstrate its applicability, metal scavengers siderophores were imaged directly from agar culture of S. wadayamensis, and well resolved and intense images were obtained using both desorption electrospray ionization (DESI) and easy ambient sonic-spray ionization (EASI) with well-defined selective spatial distributions for the free and the metal-bound molecules, providing clues for their roles in cellular metabolism.

  14. Identifying modifications in RNA by MALDI mass spectrometry

    DEFF Research Database (Denmark)

    Douthwaite, Stephen; Kirpekar, Finn

    2007-01-01

    Posttranscriptional modifications on the base or sugar of ribonucleosides generally result in mass increases that can be measured by mass spectrometry. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a direct and accurate means of determining the masses of RNAs. Mass...... spectra produced by MALDI are relatively straightforward to interpret, because they are dominated by singly charged ions, making it possible to analyze complex mixtures of RNA oligonucleotides ranging from trinucleotides up to 20-mers. Analysis of modifications within much longer RNAs, such as ribosomal...... RNAs, can be achieved by digesting the RNA with nucleotide-specific enzymes. In some cases, it may be desirable to isolate specific sequence regions before MALDI-MS analysis, and this requires a few additional steps. The method is applicable to the study of modified RNAs from cell extracts as well...

  15. Dating Studies of Elephant Tusks Using Accelerator Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Sideras-Haddad, E; Brown, T A

    2002-10-03

    A new method for determining the year of birth, the year of death, and hence, the age at death, of post-bomb and recently deceased elephants has been developed. The technique is based on Accelerator Mass Spectrometry radiocarbon analyses of small-sized samples extracted from along the length of a ge-line of an elephant tusk. The measured radiocarbon concentrations in the samples from a tusk can be compared to the {sup 14}C atmospheric bomb-pulse curve to derive the growth years of the initial and final samples from the tusk. Initial data from the application of this method to two tusks will be presented. Potentially, the method may play a significant role in wildlife management practices of African national parks. Additionally, the method may contribute to the underpinnings of efforts to define new international trade regulations, which could, in effect, decrease poaching and the killing of very young animals.

  16. Effective clean-up and ultra high-performance liquid chromatography-tandem mass spectrometry for isoflavone determination in legumes.

    Science.gov (United States)

    Vila-Donat, Pilar; Caprioli, Giovanni; Maggi, Filippo; Ricciutelli, Massimo; Torregiani, Elisabetta; Vittori, Sauro; Sagratini, Gianni

    2015-05-01

    Legumes are an excellent source of macronutrients and phytochemicals as isoflavones. The aim of this work was to develop a new analytical method for determining five isoflavone compounds, three of which are aglycons, namely daidzein, genistein, biochanin A, and two of which, daidzin and genistin, are glycosilated, in lentils and other pulses, using an effective clean-up system and UHPLC-MS/MS (triple quadrupole) method. The recoveries obtained by spiking the lentil samples with a standard mixture of isoflavones at three levels of fortification (5, 25 and 100 μg kg(-1)) were in the range of 54.4-111.1%, 68.6-91.1%, and 84.4-114%, respectively. The method was applied to analyse 48 lentil samples from central Italy and pulses for determining the isoflavone content, which was found to range from 1.1 to 95.6 μg kg(-1).

  17. Transition of Iodine Analysis to Accelerator Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Watrous, Matthew George [Idaho National Lab. (INL), Idaho Falls, ID (United States); Adamic, Mary Louise [Idaho National Lab. (INL), Idaho Falls, ID (United States); Olson, John Eric [Idaho National Lab. (INL), Idaho Falls, ID (United States); Baeck, D. L. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Fox, R. V. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Hahn, P. A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Jenson, D. D. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Lister, T. E. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-09-01

    The goal of the project, New Paradigms for Isotope Ratio Mass Spectrometry: Raising the Scientific Profile and Improved Performance for Accelerator Mass Spectrometry (AMS) and Thermal Ionization Mass Spectrometry (TIMS), is to ensure that the ongoing isotope ratio determination capability within the U.S. Department of Energy complex is the world’s best for application to nonproliferation. This report spells out the progress of Task 4, Transition of TIMS to AMS for Iodine Analysis, of the larger project. The subtasks under Task 4 and the accomplishments throughout the three year project life cycle are presented in this report. Progress was made in optimization of chemical extraction, determination of a detection limit for 127Iodine, production of standard materials for AMS analysis quality assurance, facilitation of knowledge exchange with respect to analyzing iodine on an AMS, cross comparison with a world-leading AMS laboratory, supercritical fluid extraction of iodine for AMS analysis and electrodeposition of seawater as a direct method of preparation for iodine analysis by AMS--all with the goal of minimizing the time required to stand up an AMS capability for iodine analysis of exposed air filters at INL. An effective extraction method has been developed and demonstrated for iodine analysis of exposed air filters. Innovative techniques to accomplish the cathode preparation for AMS analysis were developed and demonstrated and published. The known gap of a lack of available materials for reference standards in the analysis of iodine by AMS was filled by the preparation of homogenous materials that were calibrated against NIST materials. A minimum limit on the amount of abundant isotope in a sample was determined for AMS analysis. The knowledge exchange occurred with fantastic success. Scientists engaged the international AMS community at conferences, as well as in their laboratories for collaborative work. The supercritical fluid extraction work has positive

  18. Exploring matrix effects in liquid chromatography-tandem mass spectrometry determination of pesticide residues in tropical fruits.

    Science.gov (United States)

    Botero-Coy, Ana María; Marín, José M; Serrano, Roque; Sancho, Juan Vicente; Hernández, Félix

    2015-05-01

    Tropical fruits are being increasingly consumed around the world because of their appreciated characteristics, particularly their high nutritional value and distinctive taste, which are different from those of traditional fruits. Owing to their introduction into international markets it is necessary to have a reliable analytical methodology available for the sensitive determination of pesticide residues in order to monitor the compliance of maximum residue limits (MRLs). From an analytical point of view, tropical fruits have generally been far less studied than other fruits frequently consumed in the European Union or USA, which are among the most important markets. In this work, LC-MS/MS-based methodology using a triple quadrupole analyzer was developed for the multi-residue determination of selected pesticides and metabolites in tropical fruits, which were selected among the most popular in Colombia, one of the most important suppliers of tropical fruits around the world. After selection of a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe)-based sample treatment, the study focused on the evaluation of matrix effects, in order to find a simple way for their correction. Twelve different food matrices were selected to perform this study: the seven Colombian tropical fruits of highest value for domestic and international markets (uchuva, tamarillo, granadilla, gulupa, maracuya, papaya, and pithaya), and five more matrices highly consumed in Colombia (lulo, carambolo, feijoa, mangostan, and guayaba). Twenty compounds, including pesticides widely applied in tropical fruits pest control and several metabolites considered in residue definition, were used as model compounds in this work. Correction factors were used on the basis of calibration graphs obtained with standards in solvent and in matrix, and their usefulness was supported by validation of the method in all the matrices tested at 0.01 and 0.1 mg/kg. The analysis of real-world samples revealed the

  19. Effective identification of Akt interacting proteins by two-step chemical crosslinking, co-immunoprecipitation and mass spectrometry.

    Science.gov (United States)

    Huang, Bill X; Kim, Hee-Yong

    2013-01-01

    Akt is a critical protein for cell survival and known to interact with various proteins. However, Akt binding partners that modulate or regulate Akt activation have not been fully elucidated. Identification of Akt-interacting proteins has been customarily achieved by co-immunoprecipitation combined with western blot and/or MS analysis. An intrinsic problem of the method is loss of interacting proteins during procedures to remove non-specific proteins. Moreover, antibody contamination often interferes with the detection of less abundant proteins. Here, we developed a novel two-step chemical crosslinking strategy to overcome these problems which resulted in a dramatic improvement in identifying Akt interacting partners. Akt antibody was first immobilized on protein A/G beads using disuccinimidyl suberate and allowed to bind to cellular Akt along with its interacting proteins. Subsequently, dithiobis[succinimidylpropionate], a cleavable crosslinker, was introduced to produce stable complexes between Akt and binding partners prior to the SDS-PAGE and nanoLC-MS/MS analysis. This approach enabled identification of ten Akt partners from cell lysates containing as low as 1.5 mg proteins, including two new potential Akt interacting partners. None of these but one protein was detectable without crosslinking procedures. The present method provides a sensitive and effective tool to probe Akt-interacting proteins. This strategy should also prove useful for other protein interactions, particularly those involving less abundant or weakly associating partners.

  20. Hybrid ion mobility and mass spectrometry as a separation tool.

    Science.gov (United States)

    Ewing, Michael A; Glover, Matthew S; Clemmer, David E

    2016-03-25

    Ion mobility spectrometry (IMS) coupled to mass spectrometry (MS) has seen spectacular growth over the last two decades. Increasing IMS sensitivity and capacity with improvements in MS instrumentation have driven this growth. As a result, a diverse new set of techniques for separating ions by their mobility have arisen, each with characteristics that make them favorable for some experiments and some mass spectrometers. Ion mobility techniques can be broken down into dispersive and selective techniques based upon whether they pass through all mobilities for later analysis by mass spectrometry or select ions by mobility or a related characteristic. How ion mobility techniques fit within a more complicated separation including mass spectrometry and other techniques such as liquid chromatography is of fundamental interest to separations scientists. In this review we explore the multitude of ion mobility techniques hybridized to different mass spectrometers, detailing current challenges and opportunities for each ion mobility technique and for what experiments one technique might be chosen over another. The underlying principles of ion mobility separations, including: considerations regarding separation capabilities, ion transmission, signal intensity and sensitivity, and the impact that the separation has upon the ion structure (i.e., the possibility of configurational changes due to ion heating) are discussed.

  1. Mass Spectrometry Imaging, an Emerging Technology in Neuropsychopharmacology

    Science.gov (United States)

    Shariatgorji, Mohammadreza; Svenningsson, Per; Andrén, Per E

    2014-01-01

    Mass spectrometry imaging is a powerful tool for directly determining the distribution of proteins, peptides, lipids, neurotransmitters, metabolites and drugs in neural tissue sections in situ. Molecule-specific imaging can be achieved using various ionization techniques that are suited to different applications but which all yield data with high mass accuracies and spatial resolutions. The ability to simultaneously obtain images showing the distributions of chemical species ranging from metal ions to macromolecules makes it possible to explore the chemical organization of a sample and to correlate the results obtained with specific anatomical features. The imaging of biomolecules has provided new insights into multiple neurological diseases, including Parkinson's and Alzheimer's disease. Mass spectrometry imaging can also be used in conjunction with other imaging techniques in order to identify correlations between changes in the distribution of important chemical species and other changes in the properties of the tissue. Here we review the applications of mass spectrometry imaging in neuroscience research and discuss its potential. The results presented demonstrate that mass spectrometry imaging is a useful experimental method with diverse applications in neuroscience. PMID:23966069

  2. Metabolomic Profiling of the Effects of Melittin on Cisplatin Resistant and Cisplatin Sensitive Ovarian Cancer Cells Using Mass Spectrometry and Biolog Microarray Technology

    Directory of Open Access Journals (Sweden)

    Sanad Alonezi

    2016-10-01

    Full Text Available In the present study, liquid chromatography-mass spectrometry (LC-MS was employed to characterise the metabolic profiles of two human ovarian cancer cell lines A2780 (cisplatin-sensitive and A2780CR (cisplatin-resistant in response to their exposure to melittin, a cytotoxic peptide from bee venom. In addition, the metabolomics data were supported by application of Biolog microarray technology to examine the utilisation of carbon sources by the two cell lines. Data extraction with MZmine 2.14 and database searching were applied to provide metabolite lists. Principal component analysis (PCA gave clear separation between the cisplatin-sensitive and resistant strains and their respective controls. The cisplatin-resistant cells were slightly more sensitive to melittin than the sensitive cells with IC50 values of 4.5 and 6.8 μg/mL respectively, although the latter cell line exhibited the greatest metabolic perturbation upon treatment. The changes induced by melittin in the cisplatin-sensitive cells led mostly to reduced levels of amino acids in the proline/glutamine/arginine pathway, as well as to decreased levels of carnitines, polyamines, adenosine triphosphate (ATP and nicotinamide adenine dinucleotide (NAD+. The effects on energy metabolism were supported by the data from the Biolog assays. The lipid compositions of the two cell lines were quite different with the A2780 cells having higher levels of several ether lipids than the A2780CR cells. Melittin also had some effect on the lipid composition of the cells. Overall, this study suggests that melittin might have some potential as an adjuvant therapy in cancer treatment.

  3. Metabolomic study on the antihypertensive effect of S-1-propenylcysteine in spontaneously hypertensive rats using liquid chromatography coupled with quadrupole-Orbitrap mass spectrometry.

    Science.gov (United States)

    Matsutomo, Toshiaki; Ushijima, Mitsuyasu; Kodera, Yukihiro; Nakamoto, Masashi; Takashima, Miyuki; Morihara, Naoaki; Tamura, Koichi

    2017-03-01

    Aged garlic extract (AGE) has been shown to improve hypertension in both clinical trials and experimental animal models. However, the active ingredient of AGE remains unknown. In the present study, we investigated the antihypertensive effects of AGE and its major constituents including S-1-propenylcysteine (S1PC) and S-allylcysteine (SAC) using spontaneously hypertensive rats (SHR) and found that S1PC is an active substance to lower blood pressure in SHR. In addition, the metabolomics approach was used to investigate the potential mechanism of the antihypertensive action of S1PC in SHR. Treatment with AGE (2g/kg body weight) or S1PC (6.5mg/kg body weight; equivalent to AGE 2g/kg body weight) significantly decreased the systolic blood pressure (SBP) of SHR after the repeated administration for 10 weeks, whereas treatment with SAC (7.9mg/kg body weight; equivalent to AGE 2g/kg body weight) did not decrease the SBP. After the treatment for 10 weeks, the plasma samples obtained from Wistar Kyoto (WKY) rats and SHR were analyzed by means of ultra high performance liquid chromatography coupled with high-resolution quadrupole-Orbitrap mass spectrometry. Multivariate statistical analysis of LC-MS data showed a clear difference in the metabolite profiles between WKY rats and SHR. The results indicated that 30 endogenous metabolites significantly contributed to the difference and 7 of 30 metabolites were changed by the S1PC treatment. Furthermore, regression analysis showed correlation between SBP and the plasma levels of betaine, tryptophan and 3 LysoPCs. This metabolomics approach suggested that S1PC could exert its antihypertensive effect by affecting glycine, serine and threonine metabolism, tryptophan metabolism and glycerophospholipid metabolism.

  4. A New Accelerator-Based Mass Spectrometry.

    Science.gov (United States)

    Gove, H. E.

    1983-01-01

    Tandem electrostatic accelerators produce beams of positive ions which are used to penetrate atomic nuclei in a target, inducing nuclear reactions whose study elucidates varied properties of the nucleus. Uses of the system, which acts like a mass spectrometer, are discussed. These include radiocarbon dating measurements. (JN)

  5. Mass spectrometry on the surface of Mercury

    Science.gov (United States)

    Whitby, J.; Rohner, U.; Benz, W.; Wurz, P.

    2003-04-01

    The proposed Mercury Surface Element of the BepiColombo mission will place a lander on Mercury equipped with a geochemistry instrumentation package. We will discuss the utility of elemental and isotopic analyses of individual mineral grains in the hermean regolith, and present relevant results from a prototype laser-ablation time-of-flight mass spectrometer.

  6. Examining the Influence of Phosphorylation on Peptide Ion Structure by Ion Mobility Spectrometry-Mass Spectrometry

    Science.gov (United States)

    Glover, Matthew S.; Dilger, Jonathan M.; Acton, Matthew D.; Arnold, Randy J.; Radivojac, Predrag; Clemmer, David E.

    2016-05-01

    Ion mobility spectrometry-mass spectrometry (IMS-MS) techniques are used to study the general effects of phosphorylation on peptide structure. Cross sections for a library of 66 singly phosphorylated peptide ions from 33 pairs of positional isomers, and unmodified analogues were measured. Intrinsic size parameters (ISPs) derived from these measurements yield calculated collision cross sections for 85% of these phosphopeptide sequences that are within ±2.5% of experimental values. The average ISP for the phosphoryl group (0.64 ± 0.05) suggests that in general this moiety forms intramolecular interactions with the neighboring residues and peptide backbone, resulting in relatively compact structures. We assess the capability of ion mobility to separate positional isomers (i.e., peptide sequences that differ only in the location of the modification) and find that more than half of the isomeric pairs have >1% difference in collision cross section. Phosphorylation is also found to influence populations of structures that differ in the cis/ trans orientation of Xaa-Pro peptide bonds. Several sequences with phosphorylated Ser or Thr residues located N-terminally adjacent to Pro residues show fewer conformations compared to the unmodified sequences.

  7. High-accuracy mass spectrometry for fundamental studies.

    Science.gov (United States)

    Kluge, H-Jürgen

    2010-01-01

    Mass spectrometry for fundamental studies in metrology and atomic, nuclear and particle physics requires extreme sensitivity and efficiency as well as ultimate resolving power and accuracy. An overview will be given on the global status of high-accuracy mass spectrometry for fundamental physics and metrology. Three quite different examples of modern mass spectrometric experiments in physics are presented: (i) the retardation spectrometer KATRIN at the Forschungszentrum Karlsruhe, employing electrostatic filtering in combination with magnetic-adiabatic collimation-the biggest mass spectrometer for determining the smallest mass, i.e. the mass of the electron anti-neutrino, (ii) the Experimental Cooler-Storage Ring at GSI-a mass spectrometer of medium size, relative to other accelerators, for determining medium-heavy masses and (iii) the Penning trap facility, SHIPTRAP, at GSI-the smallest mass spectrometer for determining the heaviest masses, those of super-heavy elements. Finally, a short view into the future will address the GSI project HITRAP at GSI for fundamental studies with highly-charged ions.

  8. Laser Mass Spectrometry in Planetary Science

    Science.gov (United States)

    Wurz, P.; Whitby, J. A.; Managadze, G. G.

    2009-06-01

    Knowing the chemical, elemental, and isotopic composition of planetary objects allows the study of their origin and evolution within the context of our solar system. Exploration plans in planetary research of several space agencies consider landing spacecraft for future missions. Although there have been successful landers in the past, more landers are foreseen for Mars and its moons, Venus, the jovian moons, and asteroids. Furthermore, a mass spectrometer on a landed spacecraft can assist in the sample selection in a sample-return mission and provide mineralogical context, or identify possible toxic soils on Mars for manned Mars exploration. Given the resources available on landed spacecraft mass spectrometers, as well as any other instrument, have to be highly miniaturised.

  9. Plasma source mass spectrometry in experimental nutrition.

    Science.gov (United States)

    Barnes, R M

    1998-01-01

    The development and commercial availability of plasma ion source, specifically inductively coupled plasma, mass spectrometers (ICP-MS) have significantly extended the potential application of stable isotopes for nutritional modeling. The status of research and commercial ICP-MS instruments, and their applications and limitations for stable isotopic studies are reviewed. The consequences of mass spectroscopic resolution and measurement sensitivity obtainable with quadrupole, sector, time-of-flight, and trap instruments on stable isotope analysis are examined. Requirements for reliable isotope measurements with practical biological samples including tissues and fluids are considered. The possibility for stable isotope analysis in chemically separated compounds (speciation) also is explored. On-line compound separations by chromatography or electrophoresis, for example, have been combined instrumentally with ICP-MS. Som possibilities and requirements are described for stable isotope speciation analysis.

  10. High-Performance Liquid Chromatography-Mass Spectrometry.

    Science.gov (United States)

    Vestal, Marvin L.

    1984-01-01

    Reviews techniques for online coupling of high-performance liquid chromatography with mass spectrometry, emphasizing those suitable for application to nonvolatile samples. Also summarizes the present status, strengths, and weaknesses of various techniques and discusses potential applications of recently developed techniques for combined liquid…

  11. Decoding signalling networks by mass spectrometry-based proteomics

    DEFF Research Database (Denmark)

    Choudhary, Chuna Ram; Mann, Matthias

    2010-01-01

    Signalling networks regulate essentially all of the biology of cells and organisms in normal and disease states. Signalling is often studied using antibody-based techniques such as western blots. Large-scale 'precision proteomics' based on mass spectrometry now enables the system...

  12. Mass Spectrometry Imaging for the Classification of Tumor Tissue

    NARCIS (Netherlands)

    Mascini, N.E.

    2016-01-01

    Mass spectrometry imaging (MSI) can detect and identify many different molecules without the need for labeling. In addition, it can provide their spatial distributions as ‘molecular maps’. These features make MSI well suited for studying the molecular makeup of tumor tissue. Currently, there is an i

  13. Exploring signal transduction networks using mass spectrometry-based proteomics

    NARCIS (Netherlands)

    Meijer, L.A.T.

    2012-01-01

    Mass spectrometry (MS)-based proteomics can be used to answer a diversity of biological questions. In this thesis, we describe the application of several MS-based proteomics approaches to get insight into several aspects of signal transduction. In Chapter 2, quantitative global phosphoproteomics are

  14. Electrochemistry-mass spectrometry in drug metabolism and protein research

    NARCIS (Netherlands)

    Permentier, Hjalmar P.; Bruins, Andries P.; Bischoff, Rainer

    2008-01-01

    The combination of electrochemistry coupled on-line to mass spectrometry (EC-MS) forms a powerful analytical technique with unique applications in the fields of drug metabolism and proteomics. In this review the latest developments are surveyed from both instrumental and application perspectives. Th

  15. Characterisation of cholera toxin by liquid chromatography - Electrospray mass spectrometry

    NARCIS (Netherlands)

    Baar, B.L.M. van; Hulst, A.G.; Wils, E.R.J.

    1999-01-01

    Cholera toxin, one of the toxins that may be generated by various strains of the bacterium Vibrio cholerae, can be considered as a substance possibly used in biological warfare. The possibilities of characterising the toxin by liquid chromatography electrospray mass spectrometry (LC-ES-MS) were inve

  16. Diagnosing Prion Diseases: Mass Spectrometry-Based Approaches

    Science.gov (United States)

    Mass spectrometry is an established means of quantitating the prions present in infected hamsters. Calibration curves relating the area ratios of the selected analyte peptides and their oxidized analogs to stable isotope labeled internal standards were prepared. The limit of detection (LOD) and limi...

  17. MICELLAR ELECTROKINETIC CHROMATOGRAPHY-MASS SPECTROMETRY (R823292)

    Science.gov (United States)

    The combination of micellar electrokinetic chromatography (MEKC) with mass spectrometry (MS) is very attractive for the direct identification of analyte molecules, for the possibility of selectivity enhancement, and for the structure confirmation and analysis in a MS-MS mode. The...

  18. Traveling-wave ion mobility mass spectrometry of protein complexes

    DEFF Research Database (Denmark)

    Salbo, Rune; Bush, Matthew F; Naver, Helle

    2012-01-01

    The collision cross-section (Ω) of a protein or protein complex ion can be measured using traveling-wave (T-wave) ion mobility (IM) mass spectrometry (MS) via calibration with compounds of known Ω. The T-wave Ω-values depend strongly on instrument parameters and calibrant selection. Optimization...

  19. Characterisation of cholera toxin by liquid chromatography - Electrospray mass spectrometry

    NARCIS (Netherlands)

    Baar, B.L.M. van; Hulst, A.G.; Wils, E.R.J.

    1999-01-01

    Cholera toxin, one of the toxins that may be generated by various strains of the bacterium Vibrio cholerae, can be considered as a substance possibly used in biological warfare. The possibilities of characterising the toxin by liquid chromatography electrospray mass spectrometry (LC-ES-MS) were

  20. Mass Spectrometry Imaging for the Classification of Tumor Tissue

    NARCIS (Netherlands)

    Mascini, N.E.

    2016-01-01

    Mass spectrometry imaging (MSI) can detect and identify many different molecules without the need for labeling. In addition, it can provide their spatial distributions as ‘molecular maps’. These features make MSI well suited for studying the molecular makeup of tumor tissue. Currently, there is an i

  1. Advancing liquid chromatography- mass spectrometry based technologies for proteome research

    NARCIS (Netherlands)

    Boersema, P.J.

    2010-01-01

    In proteomics, high-tech nano-liquid chromatography (LC) and mass spectrometry (MS) instrumentation is used to routinely sequence proteins at a large scale. In this thesis, several technological developments are described to advance proteomics and their applicability is demonstrated in several diffe

  2. Gas chromatography mass spectrometry : key technology in metabolomics

    NARCIS (Netherlands)

    Koek, Maud Marijtje

    2009-01-01

    Metabolomics involves the unbiased quantitative and qualitative analysis of the complete set of metabolites present in cells, body fluids and tissues. Gas chromatography coupled to mass spectrometry (GC-MS) is very suitable for metabolomics analysis, as it combines high separation power with sensiti

  3. Fusion of mass spectrometry-based metabolomics data

    NARCIS (Netherlands)

    Smilde, A.K.; Werf, M.J. van der; Bijlsma, S.; Werff-van der Vat, B.J.C. van der; Jellema, R.H.

    2005-01-01

    A general method is presented for combining mass spectrometry-based metabolomics data. Such data are becoming more and more abundant, and proper tools for fusing these types of data sets are needed. Fusion of metabolomics data leads to a comprehensive view on the metabolome of an organism or biologi

  4. Analysis of essential oils by gas chromatography and mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Masada, Y.

    1976-01-01

    The book is in two parts: first part Essential Oil includes compositae; labiatae; verbenaceae; oleaceae; umbelliferae; myrtaceae; euphorbiaceae; rutaceae; geraniaceae; rosaceae; lauraceae; myristicaceae; anonaceae; santalaceae; moraceae; piperaceae; zingiberaceae; araceae; gramineae; and cupressaceae written in English and Japanese. Part two includes essential oil; gas chromatography, and mass spectrometry written in Japanese. (DP)

  5. Triple Bioaffinity Mass Spectrometry Concept for Thyroid Transporter Ligands

    NARCIS (Netherlands)

    Aqai, P.; Fryganas, C.; Mizuguchi, M.; Haasnoot, W.; Nielen, M.W.F.

    2012-01-01

    For the analysis of thyroid transporter ligands, a triple bioaffinity mass spectrometry (BioMS) concept was developed, with the aim at three different analytical objectives: rapid screening of any ligand, confirmation of known ligands in accordance with legislative requirements, and identification o

  6. Gas chromatography mass spectrometry : key technology in metabolomics

    NARCIS (Netherlands)

    Koek, Maud Marijtje

    2009-01-01

    Metabolomics involves the unbiased quantitative and qualitative analysis of the complete set of metabolites present in cells, body fluids and tissues. Gas chromatography coupled to mass spectrometry (GC-MS) is very suitable for metabolomics analysis, as it combines high separation power with

  7. On-Line Synthesis and Analysis by Mass Spectrometry

    Science.gov (United States)

    Bain, Ryan M.; Pulliam, Christopher J.; Raab, Shannon A.; Cooks, R. Graham

    2015-01-01

    In this laboratory experiment, students learn how to use ESI to accelerate chemical synthesis and to couple it with on-line mass spectrometry for structural analysis. The Hantzsch synthesis of symmetric 1,4-dihydropyridines is a classic example of a one-pot reaction in which multiple intermediates can serve to indicate the progress of the reaction…

  8. May the Best Molecule Win: Competition ESI Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Sarah Laughlin

    2015-10-01

    Full Text Available Electrospray ionization mass spectrometry has become invaluable in the characterization of macromolecular biological systems such as nucleic acids and proteins. Recent advances in the field of mass spectrometry and the soft conditions characteristic of electrospray ionization allow for the investigation of non-covalent interactions among large biomolecules and ligands. Modulation of genetic processes through the use of small molecule inhibitors with the DNA minor groove is gaining attention as a potential therapeutic approach. In this review, we discuss the development of a competition method using electrospray ionization mass spectrometry to probe the interactions of multiple DNA sequences with libraries of minor groove binding molecules. Such an approach acts as a high-throughput screening method to determine important information including the stoichiometry, binding mode, cooperativity, and relative binding affinity. In addition to small molecule-DNA complexes, we highlight other applications in which competition mass spectrometry has been used. A competitive approach to simultaneously investigate complex interactions promises to be a powerful tool in the discovery of small molecule inhibitors with high specificity and for specific, important DNA sequences.

  9. Mass Spectrometry Imaging for the Classification of Tumor Tissue

    NARCIS (Netherlands)

    Mascini, N.E.

    2016-01-01

    Mass spectrometry imaging (MSI) can detect and identify many different molecules without the need for labeling. In addition, it can provide their spatial distributions as ‘molecular maps’. These features make MSI well suited for studying the molecular makeup of tumor tissue. Currently, there is an

  10. On-Line Synthesis and Analysis by Mass Spectrometry

    Science.gov (United States)

    Bain, Ryan M.; Pulliam, Christopher J.; Raab, Shannon A.; Cooks, R. Graham

    2015-01-01

    In this laboratory experiment, students learn how to use ESI to accelerate chemical synthesis and to couple it with on-line mass spectrometry for structural analysis. The Hantzsch synthesis of symmetric 1,4-dihydropyridines is a classic example of a one-pot reaction in which multiple intermediates can serve to indicate the progress of the reaction…

  11. Advances in mass spectrometry driven O-glycoproteomics

    DEFF Research Database (Denmark)

    Levery, Steven B; Steentoft, Catharina; Halim, Adnan;

    2015-01-01

    BACKGROUND: Global analyses of proteins and their modifications by mass spectrometry are essential tools in cell biology and biomedical research. Analyses of glycoproteins represent particular challenges and we are only at the beginnings of the glycoproteomic era. Some of the challenges have been...

  12. Data analysis for mass spectrometry imaging : methods and applications

    NARCIS (Netherlands)

    Abdelmoula, Walid Mohamed

    2017-01-01

    In this dissertation we developed a number of automatic methods for multi-modal data registration, mainly between mass spectrometry imaging, imaging microscopy, and the Allen Brain Atlas. We have shown the importance of these methods for performing large scale preclinical biomarker discovery

  13. Analysis of proteins using DIGE and MALDI mass spectrometry

    Science.gov (United States)

    In this work the sensitivity of the quantitative proteomics approach 2D-DIGE/MS (twoDimensional Difference Gel Electrophoresis / Mass Spectrometry) was tested by detecting decreasing amounts of a specific protein at the low picomole and sub-picomole range. Sensitivity of the 2D-D...

  14. Resolving brain regions using nanostructure initiator mass spectrometry imaging

    OpenAIRE

    Lee, Do Yup; Platt, Virginia; Bowen, Ben; Louie, Katherine; Canaria, Christie; McMurray, Cynthia T.; Northen, Trent

    2012-01-01

    Specific cell types are critically implicated in a variety of neuropathologies that exhibit region-specific susceptibility. Neuronal and glial function is impaired in a host of neurodegenerative diseases. Previous reports suggest that mass spectrometry imaging has the potential to resolve cell-specific enrichment in brain regions; however, individual ions cannot resolve glial and neuronal cells within the complex structure of brain tissue. Here, we utilized a matrix-free surface mass spectrom...

  15. Measurement of boron isotopes by negative thermal ionization mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The isobaric interference for boron isotopic measurement by negative thermal ionization mass spectrometry (NTIMS) has been studied. The result shows that the CNO- is not only from the organic material, but also from nitrate in loading reagent in NTIMS. Monitoring the mass 43 ion intensity and 43/42 ratio of blank are also necessary for the boron isotopic measurement by NTIMS, other than is only boron content.

  16. Accelerator mass spectrometry as a bioanalytical tool for nutritional research

    Energy Technology Data Exchange (ETDEWEB)

    Vogel, J.S.; Turteltaub, K.W.

    1997-09-01

    Accelerator Mass Spectrometry is a mass spectrometric method of detecting long-lived radioisotopes without regard to their decay products or half-life. The technique is normally applied to geochronology, but recently has been developed for bioanalytical tracing. AMS detects isotope concentrations to parts per quadrillion, quantifying labeled biochemicals to attomole levels in milligram- sized samples. Its advantages over non-isotopeic and stable isotope labeling methods are reviewed and examples of analytical integrity, sensitivity, specificity, and applicability are provided.

  17. Layer-by-layer thin film of reduced graphene oxide and gold nanoparticles as an effective sample plate in laser-induced desorption/ionization mass spectrometry.

    Science.gov (United States)

    Kuo, Tsung-Rong; Wang, Di-Yan; Chiu, Yu-Chen; Yeh, Yun-Chieh; Chen, Wei-Ting; Chen, Ching-Hui; Chen, Chun-Wei; Chang, Huan-Cheng; Hu, Cho-Chun; Chen, Chia-Chun

    2014-01-27

    This work demonstrated a simple platform for rapid and effective surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF MS) measurements based on the layer structure of reduced graphene oxide (rGO) and gold nanoparticles. A multi-layer thin film was fabricated by alternate layer-by-layer depositions of rGO and gold nanoparticles (LBL rGO/AuNP). The flat and clean two-dimensional film was served as the sample plate and also functioned as the matrix in SALDI-TOF MS. By simply one-step deposition of analytes onto the LBL rGO/AuNP sample plate, the MS measurements of various homogeneous samples were ready to execute. The optimization of MS signal was reached by the variation of the layer numbers of rGO and gold nanoparticles. Also, the small molecules including amino acids, carbohydrates and peptides were successfully analyzed in SALDI-TOF MS using the LBL rGO/AuNP sample plate. The results showed that the signal intensity, S N(-1) ratio and reproducibility of SALDI-TOF spectra have been significantly improved in comparison to the uses of gold nanoparticles or α-cyano-4-hydroxy-cinnamic acid (CHCA) as the assisted matrixes. Taking the advantages of the unique properties of rGO and gold nanoparticles, the ready-to-use MS sample plate, which could absorb and dissipate laser energy to analytes quite efficiently and homogeneously, has shown great commercial potentials for MS applications.

  18. Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions: the effect of molecular shape on molecular assembly and ion core character.

    Science.gov (United States)

    Mitsui, Masaaki; Ando, Naoto; Nakajima, Atsushi

    2008-06-26

    Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions, (o-TP)n(-) (n = 2-100), (m-TP)n(-) (n = 2-100), and (p-TP)n(-) (n = 1-100), respectively, are conducted to investigate the effect of molecular shape on the molecular aggregation form and the resultant ion core character of the clusters. For (o-TP)n(-) and (m-TP)n(-), neither magic numbers nor discernible isomers are observed throughout the size range. Furthermore, their vertical detachment energies (VDEs) increase up to large n and depend linearly on n(-1/3), implying that they possess a three-dimensional (3D), highly reorganized structure encompassing a monomeric anion core. For (p-TP)n(-), in contrast, prominent magic numbers of n = 5, 7, 10, 12, and 14 are observed, and the VDEs show pronounced irregular shifts below n = 10, while they remain constant above n = 14 (isomer A). These results can be rationalized with two-dimensional (2D) orderings of p-TP molecules and different types of 2D shell closure at n = 7 and 14, the monomeric and multimeric anion core, respectively. Above n = 16, the new feature (isomer B) starts to appear at the higher binding side of isomer A, and it becomes dominant with n, while isomer A gradually disappears for larger sizes. In contrast to isomer A, the VDEs of isomer B continuously increase with the cluster size. This characteristic size evolution suggests that the transition to modified 2D aggregation forms from 2D ones occurs at around n = 20.

  19. Determination of polar pesticides in olive oil and olives by hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry and high resolution mass spectrometry.

    Science.gov (United States)

    Nortes-Méndez, Rocío; Robles-Molina, José; López-Blanco, Rafael; Vass, Andrea; Molina-Díaz, Antonio; Garcia-Reyes, Juan F

    2016-09-01

    This article reports the development of two HPLC-MS methods for the determination of polar pesticides in olive oil and olive samples by hydrophilic interaction liquid chromatography (HILIC) separation followed by mass spectrometry detection with tandem mass spectrometry using a triple quadrupole instrument operated in multiple reaction monitoring mode (HILIC-MS/MS) or electrospray time-of-flight mass spectrometry (HILIC-TOFMS). The selected polar pesticides included in the study were: amitrol, cyromazine, diquat, paraquat, mepiquat, trimethylsulfonium (trimesium, glyphosate counterion) and fosetyl aluminium. The simple sample treatment procedure was based on liquid partitioning with methanol. The performance of the sample extraction was evaluated in terms of recovery rates and matrix effects in both olive oil and olives matrices. The results obtained for olive oil were satisfactory while, due to the high complexity of olives, poor recovery rates were obtained for the extraction of diquat, paraquat and amitrol, although with a reasonable precision enabling its use in routine analysis. Similarly, matrix effects were minor in the case of olive oil (ca. 20% suppression average), while significantly higher suppression was observed for olives (30-50% suppression average). The studied approaches were found to be useful for the determination of the pesticides studied in olive oil and olives with limits of quantitation below 5µgkg(-1) in most cases when tandem mass spectrometry was used, thus being in compliance with MRLs set by current EU regulation.

  20. Critical comparison of mass analyzers for forensic hair analysis by ambient ionizations mass spectrometry

    NARCIS (Netherlands)

    Duvivier, W.F.; Beek, van T.A.; Nielen, M.W.F.

    2016-01-01

    Rationale
    Recently, several direct and/or ambient mass spectrometry (MS) approaches have been suggested for drugs of abuse imaging in hair. The use of mass spectrometers with insufficient selectivity could result in false-positive measurements due to isobaric interferences. Different mass analyz

  1. Application of Laser Mass Spectrometry to Art and Archaeology

    Science.gov (United States)

    Gulian, Lase Lisa E.; Callahan, Michael P.; Muliadi, Sarah; Owens, Shawn; McGovern, Patrick E.; Schmidt, Catherine M.; Trentelman, Karen A.; deVries, Mattanjah S.

    2011-01-01

    REMPI laser mass spectrometry is a combination of resonance enhanced multiphoton ionization spectroscopy and time of flight mass spectrometry, This technique enables the collection of mass specific optical spectra as well as of optically selected mass spectra. Analytes are jet-cooled by entrainment in a molecular beam, and this low temperature gas phase analysis has the benefit of excellent vibronic resolution. Utilizing this method, mass spectrometric analysis of historically relevant samples can be simplified and improved; Optical selection of targets eliminates the need for chromatography while knowledge of a target's gas phase spectroscopy allows for facile differentiation of molecules that are in the aqueous phase considered spectroscopically indistinguishable. These two factors allow smaller sample sizes than commercial MS instruments, which in turn will require less damage to objects of antiquity. We have explored methods to optimize REMPI laser mass spectrometry as an analytical tool to archaeology using theobromine and caffeine as molecular markers in Mesoamerican pottery, and are expanding this approach to the field of art to examine laccaic acid in shellacs.

  2. Capillary electrophoresis-mass spectrometry of carbohydrates.

    Science.gov (United States)

    Zaia, Joseph

    2013-01-01

    The development of methods for capillary electrophoresis (CE) with on-line mass spectrometric detection (CE/MS) is driven by the need for accurate, robust, and sensitive glycomics analysis for basic biomedicine, biomarker discovery, and analysis of recombinant protein therapeutics. One important capability is to profile glycan mixtures with respect to the patterns of substituents including sialic acids, acetate, sulfate, phosphate, and other groups. There is additional need for an MS-compatible separation system capable of resolving carbohydrate isomers. This chapter summarizes applications of CS/MS to analysis of carbohydrates, glycoproteins, and glycopeptides that have appeared since 2008. Readers are referred to recent comprehensive reviews covering earlier publications.

  3. Analysis of Milk Oligosaccharides by Mass Spectrometry.

    Science.gov (United States)

    Wu, Lauren D; Ruhaak, L Renee; Lebrilla, Carlito B

    2017-01-01

    Human milk oligosaccharides (HMOs) are a highly abundant constituent in human milk, and its protective and prebiotic properties have attracted considerable attention. HMOs have been shown to directly and indirectly benefit the overall health of the infant due to a number of functions including serving as a beneficial food for gut bacteria, block to pathogens, and aiding in brain development. Researchers are currently exploring whether these structures may act as possible disease and nutrition biomarkers. Because of this, rapid-throughput methods are desired to investigate biological activity in large patient sets. We have optimized a rapid-throughput protocol to analyze human milk oligosaccharides using micro-volumes of human breast milk for nutritional biomarkers. This method may additionally be applied to other biological fluid substrates such as plasma, urine, and feces. The protocol involves lipid separation via centrifugation, protein precipitation using ethanol, alditol reduction with sodium borohydride, and a final solid-phase extraction purification step using graphitized carbon cartridges. Samples are analyzed using HPLC-Chip/TOF-MS and data filtered on Agilent MassHunter using an in-house library. Individual structural identification is matched against a previously developed HMO library using accurate mass and retention time. Using this method will allow in-depth characterization and profiling of HMOs in large patient sets, and will ease the process of discovering significant nutritional biomarkers in human milk.

  4. Early discovery drug screening using mass spectrometry.

    Science.gov (United States)

    Siegel, Marshall M

    2002-01-01

    Electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) mass spectrometric methods useful for early discovery drug screening are reviewed. All methods described involve studies of non-covalent complexes between biopolymer receptors and small molecule ligands formed in the condensed phase. The complexes can be sprayed intact directly into the gas phase by ESI-MS using gentle experimental conditions. Gas phase screening applications are illustrated for drug ligand candidates non-covalently interacting with peptides, proteins, RNA, and DNA. In the condensed phase, the complexes can be also isolated, denatured and analyzed by ESI-MS to identify the small molecule ligands. Condensed phase drug screening examples are illustrated for the ESI-MS ancillary techniques of affinity chromatography, ultrafiltration, ultracentrifugation, gel permeation chromatography (GPC), reverse phase-high performance liquid chromatography (RP-HPLC) and capillary electrophoretic methods. Solid phase drug screening using MALDI-MS is illustrated for small molecule ligands bound to MALDI affinity probe tips and to beads. Since ESI and MALDI principally produce molecular ions, high throughput screening is achieved by analyzing mass indexed mixtures.

  5. Hands-on Electrospray Ionization-Mass Spectrometry for Upper-Level Undergraduate and Graduate Students

    Science.gov (United States)

    Stock, Naomi L.; March, Raymond E.

    2014-01-01

    Electrospray ionization-mass spectrometry (ESI-MS) is a powerful technique for the detection, identification, and quantification of organic compounds. As mass spectrometers have become more user-friendly and affordable, many students--often with little experience in mass spectrometry--find themselves needing to incorporate mass spectrometry into…

  6. Hands-on Electrospray Ionization-Mass Spectrometry for Upper-Level Undergraduate and Graduate Students

    Science.gov (United States)

    Stock, Naomi L.; March, Raymond E.

    2014-01-01

    Electrospray ionization-mass spectrometry (ESI-MS) is a powerful technique for the detection, identification, and quantification of organic compounds. As mass spectrometers have become more user-friendly and affordable, many students--often with little experience in mass spectrometry--find themselves needing to incorporate mass spectrometry into…

  7. The specific cleavage of lactone linkage to open-loop in cyclic lipopeptide during negative ESI tandem mass spectrometry: the hydrogen bond interaction effect of 4-ethyl guaiacol.

    Directory of Open Access Journals (Sweden)

    Mengzhe Guo

    Full Text Available Mass spectrometry is a valuable tool for the analysis and identification of chemical compounds, particularly proteins and peptides. Lichenysins G, the major cyclic lipopeptide of lichenysin, and the non-covalent complex of lichenysins G and 4-ethylguaiacol were investigated with negative ion ESI tandem mass spectrometry. The different fragmentation mechanisms for these compounds were investigated. Our study shows the 4-ethylguaiacol hydrogen bond with the carbonyl oxygen of the ester group in the loop of lichenysins G. With the help of this hydrogen bond interaction, the ring structure preferentially opens in lactone linkage rather than O-C bond of the ester-group to produce alcohol and ketene. Isothermal titration 1H-NMR analysis verified the hydrogen bond and determined the proportion of subject and ligand in the non-covalent complex to be 1∶1. Theoretical calculations also suggest that the addition of the ligand can affect the energy of the transition structures (TS during loop opening.

  8. Development and Evaluation of an Externally Air-Cooled Low-Flow torch and the Attenuation of Space Charge and Matrix Effects in Inductively Coupled Plasma Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Praphairaksit, Narong [Iowa State Univ., Ames, IA (United States)

    2000-09-12

    An externally air-cooled low-flow torch has been constructed and successfully demonstrated for applications in inductively coupled plasma mass spectrometry (ICP-MS). The torch is cooled by pressurized air flowing at ~70 L/min through a quartz air jacket onto the exterior of the outer tube. The outer gas flow rate and operating RF forward power are reduced considerably. Although plasmas can be sustained at the operating power as low as 400 W with a 2 L/min of outer gas flow, somewhat higher power and outer gas flows are advisable. A stable and analytical useful plasma can be obtained at 850 W with an outer gas flow rate of ~4 L/min. Under these conditions, the air-cooled plasma produces comparable sensitivities, doubly charged ion ratios, matrix effects and other analytical merits as those produced by a conventional torch while using significantly less argon and power requirements. Metal oxide ion ratios are slightly higher with the air-cooled plasma but can be mitigated by reducing the aerosol gas flow rate slightly with only minor sacrifice in analyte sensitivity. A methodology to alleviate the space charge and matrix effects in ICP-MS has been developed. A supplemental electron source adapted from a conventional electron impact ionizer is added to the base of the skimmer. Electrons supplied from this source downstream of the skimmer with suitable amount and energy can neutralize the positive ions in the beam extracted from the plasma and diminish the space charge repulsion between them. As a result, the overall ion transmission efficiency and consequent analyte ion sensitivities are significantly improved while other important analytical aspects, such as metal oxide ion ratio, doubly charged ion ratio and background ions remain relatively unchanged with the operation of this electron source. This technique not only improves the ion transmission efficiency but also minimizes the matrix effects drastically. The matrix-induced suppression of signal for even the most

  9. Development and Evaluation of an Externally Air-Cooled Low-Flow torch and the Attenuation of Space Charge and Matrix Effects in Inductively Coupled Plasma Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Praphairaksit, N.

    2000-09-12

    An externally air-cooled low-flow torch has been constructed and successfully demonstrated for applications in inductively coupled plasma mass spectrometry (ICP-MS). The torch is cooled by pressurized air flowing at {approximately}70 L/min through a quartz air jacket onto the exterior of the outer tube. The outer gas flow rate and operating RF forward power are reduced considerably. Although plasmas can be sustained at the operating power as low as 400 W with a 2 L/min of outer gas flow, somewhat higher power and outer gas flows are advisable. A stable and analytical useful plasma can be obtained at 850 W with an outer gas flow rate of {approximately}4 L/min. Under these conditions, the air-cooled plasma produces comparable sensitivities, doubly charged ion ratios, matrix effects and other analytical merits as those produced by a conventional torch while using significantly less argon and power requirements. Metal oxide ion ratios are slightly higher with the air-cooled plasma but can be mitigated by reducing the aerosol gas flow rate slightly with only minor sacrifice in analyte sensitivity. A methodology to alleviate the space charge and matrix effects in ICP-MS has been developed. A supplemental electron source adapted from a conventional electron impact ionizer is added to the base of the skimmer. Electrons supplied from this source downstream of the skimmer with suitable amount and energy can neutralize the positive ions in the beam extracted from the plasma and diminish the space charge repulsion between them. As a result, the overall ion transmission efficiency and consequent analyte ion sensitivities are significantly improved while other important analytical aspects, such as metal oxide ion ratio, doubly charged ion ratio and background ions remain relatively unchanged with the operation of this electron source. This technique not only improves the ion transmission efficiency but also minimizes the matrix effects drastically. The matrix-induced suppression

  10. Advances in structure elucidation of small molecules using mass spectrometry

    Science.gov (United States)

    Fiehn, Oliver

    2010-01-01

    The structural elucidation of small molecules using mass spectrometry plays an important role in modern life sciences and bioanalytical approaches. This review covers different soft and hard ionization techniques and figures of merit for modern mass spectrometers, such as mass resolving power, mass accuracy, isotopic abundance accuracy, accurate mass multiple-stage MS(n) capability, as well as hybrid mass spectrometric and orthogonal chromatographic approaches. The latter part discusses mass spectral data handling strategies, which includes background and noise subtraction, adduct formation and detection, charge state determination, accurate mass measurements, elemental composition determinations, and complex data-dependent setups with ion maps and ion trees. The importance of mass spectral library search algorithms for tandem mass spectra and multiple-stage MS(n) mass spectra as well as mass spectral tree libraries that combine multiple-stage mass spectra are outlined. The successive chapter discusses mass spectral fragmentation pathways, biotransformation reactions and drug metabolism studies, the mass spectral simulation and generation of in silico mass spectra, expert systems for mass spectral interpretation, and the use of computational chemistry to explain gas-phase phenomena. A single chapter discusses data handling for hyphenated approaches including mass spectral deconvolution for clean mass spectra, cheminformatics approaches and structure retention relationships, and retention index predictions for gas and liquid chromatography. The last section reviews the current state of electronic data sharing of mass spectra and discusses the importance of software development for the advancement of structure elucidation of small molecules. Electronic supplementary material The online version of this article (doi:10.1007/s12566-010-0015-9) contains supplementary material, which is available to authorized users. PMID:21289855

  11. Recent developments in Penning-trap mass spectrometry

    Science.gov (United States)

    Block, M.

    2016-06-01

    Penning-trap mass spectrometry provides atomic masses with the highest precision. At accelerator-based on-line facilities it is applied to investigate exotic radionuclides in the context of tests of fundamental symmetries, nuclear structure studies, and nuclear astrophysics research. Recent progress in slowing down radioactive ion-beams in buffer-gas cells in combination with advanced ion-manipulation techniques has paved the way to reach nuclides ever-more far from stability. In this endeavor many efforts are underway to increase the sensitivity, the efficiency, and the precision of Penning-trap mass spectrometry. In this article some recent experimental developments are addressed with the focus on the phase-imaging ion-cyclotron-resonance technique and the Fourier transform ion-cyclotron-resonance technique.

  12. Electrochemistry-mass spectrometry in drug metabolism and protein research.

    Science.gov (United States)

    Permentier, Hjalmar P; Bruins, Andries P; Bischoff, Rainer

    2008-01-01

    The combination of electrochemistry coupled on-line to mass spectrometry (EC-MS) forms a powerful analytical technique with unique applications in the fields of drug metabolism and proteomics. In this review the latest developments are surveyed from both instrumental and application perspectives. The limitations and solutions for coupling an electrochemical system to a mass spectrometer are discussed. The electrochemical mimicking of drug metabolism, specifically by Cytochrome P450, is high-lighted as an application with high biomedical relevance. The EC-MS analysis of proteins also has promising new applications for both proteomics research and biomarker discovery. EC-MS has furthermore advantages for improved analyte detection with mass spectrometry, both for small molecules and large biomolecules. Finally, potential future directions of development of the technique are briefly discussed.

  13. Determination of {sup 135}Cs by accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    MacDonald, C.M.; Charles, C.R.J. [Andre. E. Lalonde AMS Laboratory, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Department of Earth Sciences, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Zhao, X.-L.; Kieser, W.E. [Andre. E. Lalonde AMS Laboratory, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Cornett, R.J. [Andre. E. Lalonde AMS Laboratory, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Department of Earth Sciences, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Litherland, A.E. [IsoTrace Laboratory, University of Toronto, 60 St. George St., Toronto, ON M5S 1A7 (Canada)

    2015-10-15

    The ratio of anthropogenic {sup 135}Cs and {sup 137}Cs isotopes is characteristic of a uranium fission source. This research evaluates the technique of isotope dilution (yield tracing) for the purpose of quantifying {sup 135}Cs by accelerator mass spectrometry with on-line isobar separation. Interferences from Ba, Zn{sub 2}, and isotopes of equal mass to charge ratios were successfully suppressed. However, some sample crosstalk from source contamination remains. The transmission and di-fluoride ionization efficiencies of Cs isotopes were found to be 8 × 10{sup −3} and 1.7 × 10{sup −7} respectively. This quantification of {sup 135}Cs using yield tracing by accelerator mass spectrometry shows promise for future environmental sample analysis once the issues of sample crosstalk and low efficiency can be resolved.

  14. T cells recognizing a peptide contaminant undetectable by mass spectrometry

    DEFF Research Database (Denmark)

    Brezar, Vedran; Culina, Slobodan; Østerbye, Thomas

    2011-01-01

    Synthetic peptides are widely used in immunological research as epitopes to stimulate their cognate T cells. These preparations are never completely pure, but trace contaminants are commonly revealed by mass spectrometry quality controls. In an effort to characterize novel major histocompatibility...... complex (MHC) Class I-restricted ß-cell epitopes in non-obese diabetic (NOD) mice, we identified islet-infiltrating CD8+ T cells recognizing a contaminating peptide. The amount of this contaminant was so small to be undetectable by direct mass spectrometry. Only after concentration by liquid...... chromatography, we observed a mass peak corresponding to an immunodominant islet-specific glucose-6-phosphatase catalytic subunit-related protein (IGRP)(206-214) epitope described in the literature. Generation of CD8+ T-cell clones recognizing IGRP(206-214) using a novel method confirmed the identity...

  15. LILBID-mass spectrometry of the mitochondrial preprotein translocase TOM.

    Science.gov (United States)

    Mager, Frauke; Sokolova, Lucie; Lintzel, Julia; Brutschy, Bernhard; Nussberger, Stephan

    2010-11-17

    In the present work we applied a novel mass spectrometry method termed laser-induced liquid bead ion desorption mass spectrometry (LILBID-MS) to the outer mitochondrial membrane protein translocon TOM to analyze its subunit composition and stoichiometry. With TOM core complex, purified at high pH, we demonstrate that a TOM core complex of Neurospora crassa is composed of at least two Tom40 and Tom22 molecules, respectively, and more than five small Tom subunits between 5.5 and 6.4 kDa. We show that the multiprotein complex has a total molecular mass higher than 170 depending on the number of Tom5, Tom6 and Tom7 molecules bound.

  16. Radiation Biomarker Research Using Mass Spectrometry

    Science.gov (United States)

    2007-07-01

    34. Heynick Louis, N.; Johnston Sheila, A.; Mason Patrick, A., Radio frequency electromagnetic fields: cancer, mutagenesis, and genotoxicity ...their possible carcinogenic, mutagenic, and genotoxic effects. This project found, however, that according to the majority of papers published RF...P. A., Effects of blood flow on skin heating induced by millimeter wave irradiation in humans. Health Physics 2004, 86, (2), 115-120

  17. Trends in biochemical and biomedical applications of mass spectrometry

    Science.gov (United States)

    Gelpi, Emilio

    1992-09-01

    This review attempts an in-depth evaluation of progress and achievements made since the last 11th International Mass Spectrometry Conference in the application of mass spectrometric techniques to biochemistry and biomedicine. For this purpose, scientific contributions in this field at major international meetings have been monitored, together with an extensive appraisal of literature data covering the period from 1988 to 1991. A bibliometric evaluation of the MEDLINE database for this period provides a total of almost 4000 entries for mass spectrometry. This allows a detailed study of literature and geographical sources of the most frequent applications, of disciplines where mass spectrometry is most active and of types of sample and instrumentation most commonly used. In this regard major efforts according to number of publications (over 100 literature reports) are concentrated in countries like Canada, France, Germany, Italy, Japan, Sweden, UK and the USA. Also, most of the work using mass spectrometry in biochemistry and biomedicine is centred on studies on biotransformation, metabolism, pharmacology, pharmacokinetics and toxicology, which have been carried out on samples of blood, urine, plasma and tissue, by order of frequency of use. Human and animal studies appear to be evenly distributed in terms of the number of reports published in the literature in which the authors make use of experimental animals or describe work on human samples. Along these lines, special attention is given to the real usefulness of mass spectrometry (MS) technology in routine medical practice. Thus the review concentrates on evaluating the progress made in disease diagnosis and overall patient care. As regards prevailing techniques, GCMS continues to be the mainstay of the state of the art methods for multicomponent analysis, stable isotope tracer studies and metabolic profiling, while HPLC--MS and tandem MS are becoming increasingly important in biomedical research. However

  18. The effect of different acid-treatments on the age spectrum of organic matter in sediments determined by Ramped PyrOx/accelerator mass spectrometry

    Science.gov (United States)

    McNichol, A. P.; Bao, R.

    2016-02-01

    Studies of the radiocarbon and stable carbon isotopes of organic matter (OM) in sediments have become common and are an effective way to understand the fate of sedimentary OM burial in the aquatic environment. In practice, obtaining the radiocarbon and stable carbon isotopic composition in sediments requires first removing inorganic carbon by acid treatment. Two common treatments are acid rinsing and fumigation. The radiocarbon ages and stable carbon isotopic values obtained using the different acid-treatments can differ significantly, but the details of the change of organic components have received much less attention. A new approach was recently developed for radiocarbon dating of carbonate -poor and/or rich sediments using a so-called ramped pyrolysis/oxidation ("Ramped PyrOx") method in combination with accelerator mass spectrometry. Radiocarbon and stable carbon isotopic analysis of the CO2 that evolves under a linear temperature program allows separation of OC components in sediments based on their thermochemical stability (Rosenheim et al., 2008). In this preliminary study, we explore the utility of the Ramped PyrOx method for determining the effect of different acid-treatments on radiocarbon ages and carbon isotopic compositions of OM in sediments. The observations indicate that the HCl rinsing method alters OM more than fumigation in lower carbonate samples while the opposite occurs in the high carbonate samples. This result has implications for studies of the transfer of carbon from the terrestrial to the marine environment because these are samples that contain low amounts of carbonate material. Recommendations for the most appropriate way to treat these samples will be made. The loss of organic matter during the HCl rinsing in the marine carbonate poor sediments could be one of the reasons that radiocarbon ages in the labile thermal fractions were older than that processed by fumigation, whereas younger in the resistant thermal fractions. The distinct

  19. Microscale mass spectrometry systems, devices and related methods

    Energy Technology Data Exchange (ETDEWEB)

    Ramsey, John Michael

    2017-04-11

    Mass spectrometry systems or assemblies therefore include an ionizer that includes at least one planar conductor, a mass analyzer with a planar electrode assembly, and a detector comprising at least one planar conductor. The ionizer, the mass analyzer and the detector are attached together in a compact stack assembly. The stack assembly has a perimeter that bounds an area that is between about 0.01 mm.sup.2 to about 25 cm.sup.2 and the stack assembly has a thickness that is between about 0.1 mm to about 25 mm.

  20. Microscale mass spectrometry systems, devices and related methods

    Science.gov (United States)

    Ramsey, John Michael

    2016-06-21

    Mass spectrometry systems or assemblies therefore include an ionizer that includes at least one planar conductor, a mass analyzer with a planar electrode assembly, and a detector comprising at least one planar conductor. The ionizer, the mass analyzer and the detector are attached together in a compact stack assembly. The stack assembly has a perimeter that bounds an area that is between about 0.01 mm.sup.2 to about 25 cm.sup.2 and the stack assembly has a thickness that is between about 0.1 mm to about 25 mm.

  1. High Mass Accuracy and High Mass Resolving Power FT-ICR Secondary Ion Mass Spectrometry for Biological Tissue Imaging

    CERN Document Server

    Smith, Donald F; Leach, Franklin E; Robinson, Errol W; Paša-Tolić, Ljiljana; Heeren, Ron M A

    2013-01-01

    Biological tissue imaging by secondary ion mass spectrometry has seen rapid development with the commercial availability of polyatomic primary ion sources. Endogenous lipids and other small bio-molecules can now be routinely mapped on the sub-micrometer scale. Such experiments are typically performed on time-of-flight mass spectrometers for high sensitivity and high repetition rate imaging. However, such mass analyzers lack the mass resolving power to ensure separation of isobaric ions and the mass accuracy for elemental formula assignment based on exact mass measurement. We have recently reported a secondary ion mass spectrometer with the combination of a C60 primary ion gun with a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) for high mass resolving power, high mass measurement accuracy and tandem mass spectrometry capabilities. In this work, high specificity and high sensitivity secondary ion FT-ICR MS was applied to chemical imaging of biological tissue. An entire rat brain tissu...

  2. Restricted access supramolecular solvents for removal of matrix-induced ionization effects in mass spectrometry: Application to the determination of Fusarium toxins in cereals.

    Science.gov (United States)

    García-Fonseca, Sergio; Rubio, Soledad

    2016-02-01

    Ion suppression/enhancement caused by matrix effects continues being a major concern in liquid chromatography-mass spectrometry (LC-MS). This research explores the ability of a supramolecular solvent (SUPRAS) made up of inverted hexagonal aggregates of oleic acid to behave as a liquid with restricted access properties (SUPRAS-RAM). Fusarium toxins in cereals were extracted with the oleic acid-based SUPRAS-RAM prior to their quantification by LC-electrospray ionization (ESI)-ion trap-MS (LC-ESI-IT-MS) in order to investigate the capability of this solvent to remove or reduce ionization suppression and/or enhancement in the analysis of complex samples by MS. The method involved the vortex-shaking of 300 mg of cereal with 600 μL of the SUPRAS-RAM for 15 min, centrifugation for separation of the supernatant and quantitation by LC-ESI-IT-MS. Macromolecules such as proteins and carbohydrates were excluded from extraction by chemical and physical mechanisms. Extraction of analytes and sample clean-up were thus carried out in a single step. No evaporation of the extracts was needed. Method detection limits for the legislated Fusarium toxins [i.e. deoxynivalenol (DON), zearalenone (ZEA) and fumonisins B1 (FB1) and B2 (FB2)] were 15 μg kg(-1) for DON and ZEA and 8 μg kg(-1) for fumonisins. These values were far below the maximum levels set by the European Commission for these toxins in foodstuffs. The method was successfully applied to the determination of these toxins in wheat and maize harvested in the South of Spain. No contamination of Fusarium toxins was found in samples at detectable levels. Recoveries in spiked samples were in the range 87-105%, with relative standard deviations between 1 and 7%. The use of the oleic acid-based SUPRAS-RAM effectively removed matrix interferences and allowed reliable quantitation of Fusarium toxins in cereals using solvent-based calibration.

  3. Effective methylation of phosphonic acids related to chemical warfare agents mediated by trimethyloxonium tetrafluoroborate for their qualitative detection and identification by gas chromatography-mass spectrometry.

    Science.gov (United States)

    Valdez, Carlos A; Leif, Roald N; Alcaraz, Armando

    2016-08-24

    The effective methylation of phosphonic acids related to chemical warfare agents (CWAs) employing trimethyloxonium tetrafluoroborate (TMO·BF4) for their qualitative detection and identification by gas chromatography-mass spectrometry (GC-MS) is presented. The methylation occurs in rapid fashion (1 h) and can be conveniently carried out at ambient temperature, thus providing a safer alternative to the universally employed diazomethane-based methylation protocols. Optimization of the methylation parameters led us to conclude that methylene chloride was the ideal solvent to carry out the derivatization, and that even though methylated products can be observed surfacing after only 1 h, additional time was not found to be detrimental but beneficial to the process particularly when dealing with analytes at low concentrations (∼10 μg mL(-1)). Due to its insolubility in methylene chloride, TMO·BF4 conveniently settles to the bottom during the reaction and does not produce additional interfering by-products that may further complicate the GC-MS analysis. The method was demonstrated to successfully methylate a variety of Schedule 2 phosphonic acids, including their half esters, resulting in derivatives that were readily detected and identified using the instrument's spectral library. Most importantly, the method was shown to simultaneously methylate a mixture of the organophosphorus-based nerve agent hydrolysis products: pinacolyl methylphosphonate (PMPA), cyclohexyl methylphosphonate (CyMPA) and ethyl methylphosphonate (EMPA) (at a 10 μg mL(-1) concentration each) in a fatty acid ester-rich organic matrix (OPCW-PT-O3) featured in the 38th Organisation for the Prohibition of Chemical Weapons (OPCW) Proficiency Test. In addition, the protocol was found to effectively methylate N,N-diethylamino ethanesulfonic acid and N,N-diisopropylamino ethanesulfonic acid that are products arising from the oxidative degradation of the V-series agents VR and VX respectively. The

  4. Effects of metal nanoparticles on the secondary ion yields of a model alkane molecule upon atomic and polyatomic projectiles in secondary ion mass spectrometry.

    Science.gov (United States)

    Wehbe, Nimer; Heile, Andreas; Arlinghaus, Heinrich F; Bertrand, Patrick; Delcorte, Arnaud

    2008-08-15

    A model alkane molecule, triacontane, is used to assess the effects of condensed gold and silver nanoparticles on the molecular ion yields upon atomic (Ga(+) and In(+)) and polyatomic (C60(+) and Bi3(+)) ion bombardment in metal-assisted secondary ion mass spectrometry (MetA-SIMS). Molecular films spin-coated on silicon were metallized using a sputter-coater system, in order to deposit controlled quantities of gold and silver on the surface (from 0 to 15 nm equivalent thickness). The effects of gold and silver islets condensed on triacontane are also compared to the situation of thin triacontane overlayers on metallic substrates (gold and silver). The results focus primarily on the measured yields of quasi-molecular ions, such as (M - H)(+) and (2M - 2H)(+), and metal-cationized molecules, such as (M + Au)(+) and (M + Ag)(+), as a function of the quantity of metal on the surface. They confirm the absence of a simple rule to explain the secondary ion yield improvement in MetA-SIMS. The behavior is strongly dependent on the specific projectile/metal couple used for the experiment. Under atomic bombardment (Ga(+), In(+)), the characteristic ion yields an increase with the gold dose up to approximately 6 nm equivalent thickness. The yield enhancement factor between gold-metallized and pristine samples can be as large as approximately 70 (for (M - H)(+) under Ga(+) bombardment; 10 nm of Au). In contrast, with cluster projectiles such as Bi3(+) and C60(+), the presence of gold and silver leads to a dramatic molecular ion yield decrease. Cluster projectiles prove to be beneficial for triacontane overlayers spin-coated on silicon or metal substrates (Au, Ag) but not in the situation of MetA-SIMS. The fundamental difference of behavior between atomic and cluster primary ions is tentatively explained by arguments involving the different energy deposition mechanisms of these projectiles. Our results also show that Au and Ag nanoparticles do not induce the same behavior in Met

  5. Ion source memory in {sup 36}Cl accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Pavetich, Stefan; Akhmadaliev, Shavkat; Merchel, Silke; Rugel, Georg [HZDR, Dresden (Germany); Arnold, Maurice; Aumaitre, Georges; Bourles, Didier; Martschini, Martin [ASTER, Aix-en-Provence (France); Buchriegler, Josef; Golser, Robin; Keddadouche, Karim; Steier, Peter [VERA, Vienna (Austria)

    2013-07-01

    Since the DREAMS (Dresden Accelerator Mass Spectrometry) facility went operational in 2011, constant effort was put into enabling routine measurements of long-lived radionuclides as {sup 10}Be, {sup 26}Al and {sup 41}Ca. For precise AMS-measurements of the volatile element Cl the key issue is the minimization of the long term memory effect. For this purpose one of the two original HVE sources was mechanically modified, allowing the usage of bigger cathodes with individual target apertures. Additionally a more open geometry was used to improve the vacuum level. To evaluate this improvement in comparison to other up-to-date ion sources, a small inter-laboratory comparison had been initiated. The long-term memory effect in the Cs sputter ion sources of the AMS facilities VERA, ASTER and DREAMS had been investigated by running samples of natural {sup 35}Cl/{sup 37}Cl-ratio and samples containing highly enriched {sup 35}Cl({sup 35}Cl/{sup 37}Cl > 500). Primary goals of the research are the time constants of the recovery from the contaminated sample ratio to the initial ratio of the sample and the level of the long-term memory effect in the sources.

  6. Optimization of Whole-Body Zebrafish Sectioning Methods for Mass Spectrometry Imaging

    Science.gov (United States)

    Mass spectrometry imaging methods and protocols have become widely adapted to a variety of tissues and species. However, the mass spectrometry imaging literature contains minimal information on whole-body cryosection preparation for the zebrafish (Danio rerio), a model organism ...

  7. High-throughput shotgun lipidomics by quadrupole time-of-flight mass spectrometry

    DEFF Research Database (Denmark)

    Ståhlman, Marcus; Ejsing, Christer S.; Tarasov, Kirill;

    2009-01-01

    Technological advances in mass spectrometry and meticulous method development have produced several shotgun lipidomic approaches capable of characterizing lipid species by direct analysis of total lipid extracts. Shotgun lipidomics by hybrid quadrupole time-of-flight mass spectrometry allows...

  8. Implementation of suitable flow injection/sequential-sample separation/preconcentration schemes for determination of trace metal concentrations using detection by electrothermal atomic absorption spectrometry and inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Hansen, Elo Harald; Wang, Jianhua

    2002-01-01

    Various preconditioning procedures encomprising appropriate separation/preconcentration schemes in order to obtain optimal sensitivity and selectivity characteristics when using electrothermal atomic absorption spectrometry (ETAAS) and inductively coupled plasma mass spectrometry (ICPMS) are pres......Various preconditioning procedures encomprising appropriate separation/preconcentration schemes in order to obtain optimal sensitivity and selectivity characteristics when using electrothermal atomic absorption spectrometry (ETAAS) and inductively coupled plasma mass spectrometry (ICPMS...... prior to detection are effected in a microconduit placed on top of an SI selection valve....

  9. Native Mass Spectrometry: What is in the Name?

    Science.gov (United States)

    Leney, Aneika C.; Heck, Albert J. R.

    2016-12-01

    Electrospray ionization mass spectrometry (ESI-MS) is nowadays one of the cornerstones of biomolecular mass spectrometry and proteomics. Advances in sample preparation and mass analyzers have enabled researchers to extract much more information from biological samples than just the molecular weight. In particular, relevant for structural biology, noncovalent protein-protein and protein-ligand complexes can now also be analyzed by MS. For these types of analyses, assemblies need to be retained in their native quaternary state in the gas phase. This initial small niche of biomolecular mass spectrometry, nowadays often referred to as "native MS," has come to maturation over the last two decades, with dozens of laboratories using it to study mostly protein assemblies, but also DNA and RNA-protein assemblies, with the goal to define structure-function relationships. In this perspective, we describe the origins of and (re)define the term native MS, portraying in detail what we meant by "native MS," when the term was coined and also describing what it does (according to us) not entail. Additionally, we describe a few examples highlighting what native MS is, showing its successes to date while illustrating the wide scope this technology has in solving complex biological questions.

  10. Native Mass Spectrometry: What is in the Name?

    Science.gov (United States)

    Leney, Aneika C.; Heck, Albert J. R.

    2017-01-01

    Electrospray ionization mass spectrometry (ESI-MS) is nowadays one of the cornerstones of biomolecular mass spectrometry and proteomics. Advances in sample preparation and mass analyzers have enabled researchers to extract much more information from biological samples than just the molecular weight. In particular, relevant for structural biology, noncovalent protein-protein and protein-ligand complexes can now also be analyzed by MS. For these types of analyses, assemblies need to be retained in their native quaternary state in the gas phase. This initial small niche of biomolecular mass spectrometry, nowadays often referred to as "native MS," has come to maturation over the last two decades, with dozens of laboratories using it to study mostly protein assemblies, but also DNA and RNA-protein assemblies, with the goal to define structure-function relationships. In this perspective, we describe the origins of and (re)define the term native MS, portraying in detail what we meant by "native MS," when the term was coined and also describing what it does (according to us) not entail. Additionally, we describe a few examples highlighting what native MS is, showing its successes to date while illustrating the wide scope this technology has in solving complex biological questions.

  11. Advances in 193 nm excimer lasers for mass spectrometry applications

    Science.gov (United States)

    Delmdahl, Ralph; Esser, Hans-Gerd; Bonati, Guido

    2016-03-01

    Ongoing progress in mass analysis applications such as laser ablation inductively coupled mass spectrometry of solid samples and ultraviolet photoionization mediated sequencing of peptides and proteins is to a large extent driven by ultrashort wavelength excimer lasers at 193 nm. This paper will introduce the latest improvements achieved in the development of compact high repetition rate excimer lasers and elaborate on the impact on mass spectrometry instrumentation. Various performance and lifetime measurements obtained in a long-term endurance test over the course of 18 months will be shown and discussed in view of the laser source requirements of different mass spectrometry tasks. These sampling type applications are served by excimer lasers delivering pulsed 193 nm output of several mJ as well as fast repetition rates which are already approaching one Kilohertz. In order to open up the pathway from the laboratory to broader market industrial use, sufficient component lifetimes and long-term stable performance behavior have to be ensured. The obtained long-term results which will be presented are based on diverse 193 nm excimer laser tube improvements aiming at e.g. optimizing the gas flow dynamics and have extended the operational life the laser tube for the first time over several billion pulses even under high duty-cycle conditions.

  12. New Types of Ionization Sources for Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    None

    2008-12-01

    The purpose of this Cooperative Research and Development Agreement (CRADA) between UT-Battelle (Contractor) and MDS Sciex (Participant) and ESA, Inc. (Participant) is to research, develop and apply new types of ionization sources and sampling/inlet systems for analytical mass spectrometry making use of the Participants state-of-the-art atmospheric sampling mass spectrometry electrochemical cell technology instrumentation and ancillary equipment. The two overriding goals of this research project are: to understand the relationship among the various instrumental components and operational parameters of the various ion sources and inlet systems under study, the chemical nature of the gases, solvents, and analytes in use, and the nature and abundances of the ions ultimately observed in the mass spectrometer; and to develop new and better analytical and fundamental applications of these ion sources and inlet systems or alternative sources and inlets coupled with mass spectrometry on the basis of the fundamental understanding obtained in Goal 1. The end results of this work are expected to be: (1) an expanded utility for the ion sources and inlet systems under study (such as the analysis of new types of analytes) and the control or alteration of the ionic species observed in the gas-phase; (2) enhanced instrument performance as judged by operational figures-of-merit such as dynamic range, detection limits, susceptibility to matrix signal suppression and sensitivity; and (3) novel applications (such as surface sampling with electrospray) in both applied and fundamental studies. The research projects outlined herein build upon work initiated under the previous CRADA between the Contractor and MDS Sciex on ion sources and inlet systems for mass spectrometry. Specific ion source and inlet systems for exploration of the fundamental properties and practical implementation of these principles are given.

  13. Ambient Mass Spectrometry Imaging Using Direct Liquid Extraction Techniques

    Energy Technology Data Exchange (ETDEWEB)

    Laskin, Julia; Lanekoff, Ingela

    2015-11-13

    Mass spectrometry imaging (MSI) is a powerful analytical technique that enables label-free spatial localization and identification of molecules in complex samples.1-4 MSI applications range from forensics5 to clinical research6 and from understanding microbial communication7-8 to imaging biomolecules in tissues.1, 9-10 Recently, MSI protocols have been reviewed.11 Ambient ionization techniques enable direct analysis of complex samples under atmospheric pressure without special sample pretreatment.3, 12-16 In fact, in ambient ionization mass spectrometry, sample processing (e.g., extraction, dilution, preconcentration, or desorption) occurs during the analysis.17 This substantially speeds up analysis and eliminates any possible effects of sample preparation on the localization of molecules in the sample.3, 8, 12-14, 18-20 Venter and co-workers have classified ambient ionization techniques into three major categories based on the sample processing steps involved: 1) liquid extraction techniques, in which analyte molecules are removed from the sample and extracted into a solvent prior to ionization; 2) desorption techniques capable of generating free ions directly from substrates; and 3) desorption techniques that produce larger particles subsequently captured by an electrospray plume and ionized.17 This review focuses on localized analysis and ambient imaging of complex samples using a subset of ambient ionization methods broadly defined as “liquid extraction techniques” based on the classification introduced by Venter and co-workers.17 Specifically, we include techniques where analyte molecules are desorbed from solid or liquid samples using charged droplet bombardment, liquid extraction, physisorption, chemisorption, mechanical force, laser ablation, or laser capture microdissection. Analyte extraction is followed by soft ionization that generates ions corresponding to intact species. Some of the key advantages of liquid extraction techniques include the ease

  14. Accelerator mass spectrometry in biomedical research

    Science.gov (United States)

    Vogel, J. S.; Turteltaub, K. W.

    1994-06-01

    Biological effects occur in natural systems at chemical concentrations of parts per billion (1:10 9) or less. Affected biomolecules may be separable in only milligram or microgram quantities. Quantification at attomole sensitivity is needed to study these interactions. AMS measures isotope concentrations to parts per 10 13-15 on milligram-sized samples and is ideal for quantifying long-lived radioisotopic labels for tracing biochemical pathways in natural systems. 14C-AMS has now been coupled to a variety of organic separation and definition technologies. Our primary research investigates pharmacokinetics and genotoxicities of toxins and drugs at very low doses. Human subjects research using AMS includes nutrition, toxicity and elemental balance studies. 3H, 41Ca and 26Al are also traced by AMS for fundamental biochemical kinetic research. Expansion of biomedical AMS awaits further development of biochemical and accelerator technologies designed specifically for these applications.

  15. Accelerator mass spectrometry in biomedical research

    Energy Technology Data Exchange (ETDEWEB)

    Vogel, J.S.; Turteltaub, K.W.

    1993-10-20

    Biological effects occur in natural systems at chemical concentrations of parts per billion (1:10{sup 9}) or less. Affected biomolecules may be separable in only milligram or microgram quantities. Quantification at attomole sensitivity is needed to study these interactions. AMS measures isotope concentrations to parts per 10{sup 13--15} on milligram-sized samples and is ideal for quantifying long-lived radioisotopic labels that are commonly used to trace biochemical pathways in natural systems. {sup 14}C-AMS has now been coupled to a variety of organic separation and definition technologies. The primary research investigates pharmacokinetics and genotoxicities of toxins and drugs at very low doses. Human subject research using AMS includes nutrition, toxicity and elemental balance studies. {sup 3} H, {sup 41}Ca and {sup 26}Al are also traced by AMS for fundamental biochemical kinetic research. Expansion of biomedical AMS awaits further development of biochemical and accelerator technologies designed specifically for these applications.

  16. Effect of mobile phase additives on qualitative and quantitative analysis of ginsenosides by liquid chromatography hybrid quadrupole-time of flight mass spectrometry.

    Science.gov (United States)

    Liang, Yan; Guan, Tianye; Zhou, Yuanyuan; Liu, Yanna; Xing, Lu; Zheng, Xiao; Dai, Chen; Du, Ping; Rao, Tai; Zhou, Lijun; Yu, Xiaoyi; Hao, Kun; Xie, Lin; Wang, Guangji

    2013-07-05

    This study was to systematically investigate the effect of mobile phase additives, including ammonia water, formic acid, acetic acid, ammonium chloride and water (as a control), on qualitative and quantitative analysis of fifteen representative ginsenosides based on liquid chromatography hybrid quadrupole-time of flight mass spectrometry (LC-Q-TOF/MS). To evaluate the influence of mobile phase additives on qualitative performance, the quality of the negative mode MS/MS spectra of ginsenosides produced by online LC-Q-TOF/MS analyses, particularly the numbers and intensities of fragment ions, were compared under different adduct ion states, and found to be strongly affected by the mobile phase additives. When 0.02% acetic acid was added in the mobile phase, the deprotonated ginsenosides ions produced the most abundant product ions, while almost no product ion was observed for the chlorinated ginsenoside ions when 0.1mM ammonium chloride was used as the mobile phase additive. On the other hand, sensitivity, linear range and precision were adopted to investigate the quantitative performance affected by different mobile phase additives. Validation results of the LC-Q-TOF/MS-based quantitative performance for ginsenosides showed that ammonium chloride not only provided the highest sensitivity for all the target analytes, but also dramatically improved the linear ranges, the intra-day and inter-day precisions comparing to the results obtained using other mobile phase additives. Importantly, the validated method, using 0.1mM ammonium chloride as the mobile phase additive, was successfully applied to the quantitative analysis of ginsenosides in rat plasma after intragastric administration of Ginsenoside Extract at 200mg/kg. In conclusion, 0.02% acetic acid was deemed to be the most suitable mobile phase additive for qualitative analysis of ginsenosides, and 0.1mM ammonium chloride in mobile phase could lead to the best quantitative performance. Our results reveal that

  17. Fourier Transform Mass Spectrometry: The Transformation of Modern Environmental Analyses

    Directory of Open Access Journals (Sweden)

    Lucy Lim

    2016-01-01

    Full Text Available Unknown compounds in environmental samples are difficult to identify using standard mass spectrometric methods. Fourier transform mass spectrometry (FTMS has revolutionized how environmental analyses are performed. With its unsurpassed mass accuracy, high resolution and sensitivity, researchers now have a tool for difficult and complex environmental analyses. Two features of FTMS are responsible for changing the face of how complex analyses are accomplished. First is the ability to quickly and with high mass accuracy determine the presence of unknown chemical residues in samples. For years, the field has been limited by mass spectrometric methods that were based on knowing what compounds of interest were. Secondly, by utilizing the high resolution capabilities coupled with the low detection limits of FTMS, analysts also could dilute the sample sufficiently to minimize the ionization changes from varied matrices.

  18. The Use of Gas Chromatography and Mass Spectrometry to Introduce General Chemistry Students to Percent Mass and Atomic Mass Calculations

    Science.gov (United States)

    Pfennig, Brian W.; Schaefer, Amy K.

    2011-01-01

    A general chemistry laboratory experiment is described that introduces students to instrumental analysis using gas chromatography-mass spectrometry (GC-MS), while simultaneously reinforcing the concepts of mass percent and the calculation of atomic mass. Working in small groups, students use the GC to separate and quantify the percent composition…

  19. The Use of Gas Chromatography and Mass Spectrometry to Introduce General Chemistry Students to Percent Mass and Atomic Mass Calculations

    Science.gov (United States)

    Pfennig, Brian W.; Schaefer, Amy K.

    2011-01-01

    A general chemistry laboratory experiment is described that introduces students to instrumental analysis using gas chromatography-mass spectrometry (GC-MS), while simultaneously reinforcing the concepts of mass percent and the calculation of atomic mass. Working in small groups, students use the GC to separate and quantify the percent composition…

  20. 'Moringa oleifera: study of phenolics and glucosinolates by mass spectrometry'.

    Science.gov (United States)

    Maldini, Mariateresa; Maksoud, Salwa A; Natella, Fausta; Montoro, Paola; Petretto, Giacomo Luigi; Foddai, Marzia; De Nicola, Gina Rosalinda; Chessa, Mario; Pintore, Giorgio

    2014-09-01

    Moringa oleifera is a medicinal plant and an excellent dietary source of micronutrients (vitamins and minerals) and health-promoting phytochemicals (phenolic compounds, glucosinolates and isothiocyanates). Glucosinolates and isothiocyanates are known to possess anti-carcinogenic and antioxidant effects and have attracted great interest from both toxicological and pharmacological points of view, as they are able to induce phase 2 detoxification enzymes and to inhibit phase 1 activation enzymes. Phenolic compounds possess antioxidant properties and may exert a preventative effect in regards to the development of chronic degenerative diseases. The aim of this work was to assess the profile and the level of bioactive compounds in all parts of M. oleifera seedlings, by using different MS approaches. First, flow injection electrospray ionization mass spectrometry (FI-ESI-MS) fingerprinting techniques and chemometrics (PCA) were used to achieve the characterization of the different plant's organs in terms of profile of phenolic compounds and glucosinolates. Second, LC-MS and LC-MS/MS qualitative and quantitative methods were used for the identification and/or determination of phenolics and glucosinolates in M. oleifera.

  1. Analytical validation of accelerator mass spectrometry for pharmaceutical development.

    Science.gov (United States)

    Keck, Bradly D; Ognibene, Ted; Vogel, John S

    2010-03-01

    The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of (14)C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the (14)C label), stable across samples storage conditions for at least 1 year, linear over four orders of magnitude with an analytical range from 0.1 Modern to at least 2000 Modern (instrument specific). Furthermore, accuracy was excellent (between 1 and 3%), while precision expressed as coefficient of variation was between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of (14)C, respectively (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with (14)C corresponds to 30 fg equivalents. Accelerator mass spectrometry provides a sensitive, accurate and precise method of measuring drug compounds in biological matrices.

  2. Proteomics and Mass Spectrometry for Cancer Biomarker Discovery

    Science.gov (United States)

    Lu, Ming; Faull, Kym F.; Whitelegge, Julian P.; He, Jianbo; Shen, Dejun; Saxton, Romaine E.; Chang, Helena R.

    2007-01-01

    Proteomics is a rapidly advancing field not only in the field of biology but also in translational cancer research. In recent years, mass spectrometry and associated technologies have been explored to identify proteins or a set of proteins specific to a given disease, for the purpose of disease detection and diagnosis. Such biomarkers are being investigated in samples including cells, tissues, serum/plasma, and other types of body fluids. When sufficiently refined, proteomic technologies may pave the way for early detection of cancer or individualized therapy for cancer. Mass spectrometry approaches coupled with bioinformatic tools are being developed for biomarker discovery and validation. Understanding basic concepts and application of such technology by investigators in the field may accelerate the clinical application of protein biomarkers in disease management. PMID:19662217

  3. Quantitative aspects of inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Bulska, Ewa; Wagner, Barbara

    2016-10-01

    Accurate determination of elements in various kinds of samples is essential for many areas, including environmental science, medicine, as well as industry. Inductively coupled plasma mass spectrometry (ICP-MS) is a powerful tool enabling multi-elemental analysis of numerous matrices with high sensitivity and good precision. Various calibration approaches can be used to perform accurate quantitative measurements by ICP-MS. They include the use of pure standards, matrix-matched standards, or relevant certified reference materials, assuring traceability of the reported results. This review critically evaluates the advantages and limitations of different calibration approaches, which are used in quantitative analyses by ICP-MS. Examples of such analyses are provided. This article is part of the themed issue 'Quantitative mass spectrometry'.

  4. Recent directions of electrospray mass spectrometry for elemental speciation analysis

    Energy Technology Data Exchange (ETDEWEB)

    Schaumloeffel, Dirk [Universite de Pau et des Pays de l' Adour/CNRS UMR 5254, Laboratoire de Chimie Analytique Bio-Inorganique et Environnement/IPREM, Pau (France); Tholey, Andreas [Christian-Albrechts-Universitaet, Institute for Experimental Medicine - Div. Systematic Proteome Research, Kiel (Germany)

    2011-06-15

    A brief survey is given of the last 2 years' literature on electrospray mass spectrometry (ESI-MS) for speciation analysis. As observed for many years, the main recent applications in this field concern arsenic and selenium species, especially in studies encompassing combined use of molecular and element mass spectrometry. A further application field is the stoichiometric characterization of metal complexes by ESI-MS, which in some studies was assisted by nuclear magnetic resonance spectroscopy. A few examples are presented to illustrate arsenic species involved in metabolic pathways, sulfur species in oils and bitumen, and aluminum complexes. On the basis of this review, we also give an outlook of expected future developments and trends in this research field. (orig.)

  5. Protein identification using nano liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Negroni, Luc

    2007-01-01

    Tandem mass spectrometry is an efficient technique for the identification of peptides on the basis of their fragmentation pattern (MS/MS scan). It can generate individual spectra for each peptide, thereby creating a powerful tool for protein identification on the basis of peptide characterization. This important advance in automatic data acquisition has allowed an efficient association between liquid chromatography and tandem mass spectrometry, and the use of nanocolumns and nanoelectrospray ionization has dramatically increased the efficiency of this method. Now large sets of peptides can be identified at a femtomole level. At the end of the process, batch processing of the MS/MS spectra produces peptide lists that identify purified proteins or protein mixtures with high confidence.

  6. Analysis of Protein O-GlcNAcylation by Mass Spectrometry.

    Science.gov (United States)

    Ma, Junfeng; Hart, Gerald W

    2017-02-02

    O-linked β-D-N-acetyl glucosamine (O-GlcNAc) addition (O-GlcNAcylation), a post-translational modification of serine/threonine residues of proteins, is involved in diverse cellular metabolic and signaling pathways. Aberrant O-GlcNAcylation underlies the initiation and progression of multiple chronic diseases including diabetes, cancer, and neurodegenerative diseases. Numerous methods have been developed for the analysis of protein O-GlcNAcylation, but instead of discussing the classical biochemical techniques, this unit covers O-GlcNAc characterization by combining several enrichment methods and mass spectrometry detection techniques [including collision-induced dissociation (CID), higher energy collision dissociation (HCD), and electron transfer dissociation (ETD) mass spectrometry]. © 2017 by John Wiley & Sons, Inc.

  7. Metabolome analysis - mass spectrometry and microbial primary metabolites

    DEFF Research Database (Denmark)

    Højer-Pedersen, Jesper Juul

    2008-01-01

    that are highly sensitive and specific, and to undertake this challenge mass spectrometry (MS) is among the best candidates. Along with analysis of the metabolome the research area of metabolomics has evolved. Metabolomics combines metabolite profiles, data mining and biochemistry and aims at understanding...... the interplay between metabolites. In this thesis, different topics have been addressed and discussed with the aim of advancing metabolomics to explore the concept in a physiological context. The metabolome comprises a wide variety of chemical compounds that act differently upon sample preparation...... glucose, galactose or ethanol, and metabolic footprinting by mass spectrometry was used to study the influence of carbon source on the extracellular metabolites. The results showed that footprints clustered according to the carbon source. Advances in technologies for analytical chemistry have mediated...

  8. Sharing and community curation of mass spectrometry data with GNPS

    Science.gov (United States)

    Nguyen, Don Duy; Watrous, Jeramie; Kapono, Clifford A; Luzzatto-Knaan, Tal; Porto, Carla; Bouslimani, Amina; Melnik, Alexey V; Meehan, Michael J; Liu, Wei-Ting; Crüsemann, Max; Boudreau, Paul D; Esquenazi, Eduardo; Sandoval-Calderón, Mario; Kersten, Roland D; Pace, Laura A; Quinn, Robert A; Duncan, Katherine R; Hsu, Cheng-Chih; Floros, Dimitrios J; Gavilan, Ronnie G; Kleigrewe, Karin; Northen, Trent; Dutton, Rachel J; Parrot, Delphine; Carlson, Erin E; Aigle, Bertrand; Michelsen, Charlotte F; Jelsbak, Lars; Sohlenkamp, Christian; Pevzner, Pavel; Edlund, Anna; McLean, Jeffrey; Piel, Jörn; Murphy, Brian T; Gerwick, Lena; Liaw, Chih-Chuang; Yang, Yu-Liang; Humpf, Hans-Ulrich; Maansson, Maria; Keyzers, Robert A; Sims, Amy C; Johnson, Andrew R.; Sidebottom, Ashley M; Sedio, Brian E; Klitgaard, Andreas; Larson, Charles B; P., Cristopher A Boya; Torres-Mendoza, Daniel; Gonzalez, David J; Silva, Denise B; Marques, Lucas M; Demarque, Daniel P; Pociute, Egle; O'Neill, Ellis C; Briand, Enora; Helfrich, Eric J. N.; Granatosky, Eve A; Glukhov, Evgenia; Ryffel, Florian; Houson, Hailey; Mohimani, Hosein; Kharbush, Jenan J; Zeng, Yi; Vorholt, Julia A; Kurita, Kenji L; Charusanti, Pep; McPhail, Kerry L; Nielsen, Kristian Fog; Vuong, Lisa; Elfeki, Maryam; Traxler, Matthew F; Engene, Niclas; Koyama, Nobuhiro; Vining, Oliver B; Baric, Ralph; Silva, Ricardo R; Mascuch, Samantha J; Tomasi, Sophie; Jenkins, Stefan; Macherla, Venkat; Hoffman, Thomas; Agarwal, Vinayak; Williams, Philip G; Dai, Jingqui; Neupane, Ram; Gurr, Joshua; Rodríguez, Andrés M. C.; Lamsa, Anne; Zhang, Chen; Dorrestein, Kathleen; Duggan, Brendan M; Almaliti, Jehad; Allard, Pierre-Marie; Phapale, Prasad; Nothias, Louis-Felix; Alexandrov, Theodore; Litaudon, Marc; Wolfender, Jean-Luc; Kyle, Jennifer E; Metz, Thomas O; Peryea, Tyler; Nguyen, Dac-Trung; VanLeer, Danielle; Shinn, Paul; Jadhav, Ajit; Müller, Rolf; Waters, Katrina M; Shi, Wenyuan; Liu, Xueting; Zhang, Lixin; Knight, Rob; Jensen, Paul R; Palsson, Bernhard O; Pogliano, Kit; Linington, Roger G; Gutiérrez, Marcelino; Lopes, Norberto P; Gerwick, William H; Moore, Bradley S; Dorrestein, Pieter C; Bandeira, Nuno

    2017-01-01

    The potential of the diverse chemistries present in natural products (NP) for biotechnology and medicine remains untapped because NP databases are not searchable with raw data and the NP community has no way to share data other than in published papers. Although mass spectrometry techniques are well-suited to high-throughput characterization of natural products, there is a pressing need for an infrastructure to enable sharing and curation of data. We present Global Natural Products Social molecular networking (GNPS, http://gnps.ucsd.edu), an open-access knowledge base for community wide organization and sharing of raw, processed or identified tandem mass (MS/MS) spectrometry data. In GNPS crowdsourced curation of freely available community-wide reference MS libraries will underpin improved annotations. Data-driven social-networking should facilitate identification of spectra and foster collaborations. We also introduce the concept of ‘living data’ through continuous reanalysis of deposited data. PMID:27504778

  9. Challenges ahead for mass spectrometry and proteomics applications in epigenetics.

    Science.gov (United States)

    Kessler, Benedikt M

    2010-02-01

    Inheritance of biological information to future generations depends on the replication of DNA and the Mendelian principle of distribution of genes. In addition, external and environmental factors can influence traits that can be propagated to offspring, but the molecular details of this are only beginning to be understood. The discoveries of DNA methylation and post-translational modifications on chromatin and histones provided entry points for regulating gene expression, an area now defined as epigenetics and epigenomics. Mass spectrometry turned out to be instrumental in uncovering molecular details involved in these processes. The central role of histone post-translational modifications in epigenetics related biological processes has revitalized mass spectrometry based investigations. In this special report, current approaches and future challenges that lay ahead due to the enormous complexity are discussed.

  10. Native Mass Spectrometry in Fragment-Based Drug Discovery

    Directory of Open Access Journals (Sweden)

    Liliana Pedro

    2016-07-01

    Full Text Available The advent of native mass spectrometry (MS in 1990 led to the development of new mass spectrometry instrumentation and methodologies for the analysis of noncovalent protein–ligand complexes. Native MS has matured to become a fast, simple, highly sensitive and automatable technique with well-established utility for fragment-based drug discovery (FBDD. Native MS has the capability to directly detect weak ligand binding to proteins, to determine stoichiometry, relative or absolute binding affinities and specificities. Native MS can be used to delineate ligand-binding sites, to elucidate mechanisms of cooperativity and to study the thermodynamics of binding. This review highlights key attributes of native MS for FBDD campaigns.

  11. Yield effects on 2-methoxy-3-isobutylpyrazine concentration in cabernet sauvignon using a solid phase microextraction gas chromatography/mass spectrometry method.

    Science.gov (United States)

    Chapman, Dawn M; Thorngate, John H; Matthews, Mark A; Guinard, Jean-Xavier; Ebeler, Susan E

    2004-08-25

    A rapid and automated solid phase microextraction (SPME) stable isotope dilution gas chromatography/mass spectrometry (GC-MS) method for 2-methoxy-3-isobutylpyrazine (MIBP) quantification in red wine was developed. Wines with 30% (w/v) NaCl and 2-methoxy-(2)H(3)-3-isobutylpyrazine internal standard were sampled with a 2 cm divinylbenzene/carboxen/poly(dimethylsiloxane) SPME fiber for 30 min at 40 degrees C and analyzed by GC-MS. The method was used to measure MIBP concentrations in Cabernet Sauvignon wines that were produced from six winter pruning treatments over two vintages. MIBP concentrations were significantly negatively correlated with buds per vine. In addition, the MIBP concentration was directly related to sensory vegetal intensity ratings obtained by descriptive analysis.

  12. Methods of gas purification and effect on the ion composition in an RF atmospheric pressure plasma jet investigated by mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Grosse-Kreul, Simon; Huebner, Simon; Schneider, Simon; Keudell, Achim von; Benedikt, Jan [Ruhr-Universitaet Bochum, Institute for Experimental Physics II, Bochum (Germany)

    2016-12-15

    The analysis of the ion chemistry of atmospheric pressure plasmas is essential to evaluate ionic reaction pathways during plasma-surface or plasma-analyte interactions. In this contribution, the ion chemistry of a radio-frequency atmospheric pressure plasma jet (μ-APPJ) operated in helium is investigated by mass spectrometry (MS). It is found, that the ion composition is extremely sensitive to impurities such as N{sub 2}, O{sub 2} and H{sub 2}O. Without gas purification, protonated water cluster ions of the form H{sup +}(H{sub 2}O){sub n} are dominating downstream the positive ion mass spectrum. However, even after careful feed gas purification to the sub-ppm level using a molecular sieve trap and a liquid nitrogen trap as well as operation of the plasma in a controlled atmosphere, the positive ion mass spectrum is strongly influenced by residual trace gases. The observations support the idea that species with a low ionization energy serve as a major source of electrons in atmospheric pressure helium plasmas. Similarly, the neutral density of atomic nitrogen measured by MS in a He/N{sub 2} mixture is varying up to a factor 3, demonstrating the significant influence of impurities on the neutral species chemistry as well. (orig.)

  13. Practical aspects of trapped ion mass spectrometry, 5 applications of ion trapping devices

    CERN Document Server

    March, Raymond E

    2009-01-01

    Examines ion/neutral and ion/ion reactions, ion spectroscopy, and the structural characterization of proteins and peptides using quadropole ion trap mass spectrometry, Fourier transform - ion cyclotron resonance (FT-ICR) mass spectrometry, and traveling wave ion mobility mass spectrometry.

  14. Determining the topology of virus assembly intermediates using ion mobility spectrometry-mass spectrometry.

    Science.gov (United States)

    Knapman, Tom W; Morton, Victoria L; Stonehouse, Nicola J; Stockley, Peter G; Ashcroft, Alison E

    2010-10-30

    We have combined ion mobility spectrometry-mass spectrometry with tandem mass spectrometry to characterise large, non-covalently bound macromolecular complexes in terms of mass, shape (cross-sectional area) and stability (dissociation) in a single experiment. The results indicate that the quaternary architecture of a complex influences its residual shape following removal of a single subunit by collision-induced dissociation tandem mass spectrometry. Complexes whose subunits are bound to several neighbouring subunits to create a ring-like three-dimensional (3D) architecture undergo significant collapse upon dissociation. In contrast, subunits which have only a single neighbouring subunit within a complex retain much of their original shape upon complex dissociation. Specifically, we have determined the architecture of two transient, on-pathway intermediates observed during in vitro viral capsid assembly. Knowledge of the mass, stoichiometry and cross-sectional area of each viral assembly intermediate allowed us to model a range of potential structures based on the known X-ray structure of the coat protein building blocks. Comparing the cross-sectional areas of these potential architectures before and after dissociation provided tangible evidence for the assignment of the topologies of the complexes, which have been found to encompass both the 3-fold and the 5-fold symmetry axes of the final icosahedral viral shell. Such insights provide unique information about virus assembly pathways that could allow the design of anti-viral therapeutics directed at the assembly step. This methodology can be readily applied to the structural characterisation of many other non-covalently bound macromolecular complexes and their assembly pathways.

  15. Accelerator mass spectrometry – from DNA to astrophysics

    Directory of Open Access Journals (Sweden)

    Kutschera Walter

    2013-12-01

    Full Text Available A brief review of accelerator mass spectrometry (AMS is presented. The present work touches on a few technical aspects and recent developments of AMS, and describes two specific applications of AMS, the dating of human DNA with the 14C bomb peak and the search for superheavy elements in nature. Since two extended general reviews on technical developments in AMS [1] and applications of AMS [2] will appear in 2013, frequent reference to these reviews is made.

  16. Nanostructure-initiator mass spectrometry metabolite analysis and imaging.

    Science.gov (United States)

    Greving, Matthew P; Patti, Gary J; Siuzdak, Gary

    2011-01-01

    Nanostructure-Initiator Mass Spectrometry (NIMS) is a matrix-free desorption/ionization approach that is particularly well-suited for unbiased (untargeted) metabolomics. An overview of the NIMS technology and its application in the detection of biofluid and tissue metabolites are presented. (To listen to a podcast about this feature, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html .).

  17. Fluorescence preselection of bioaerosol for single-particle mass spectrometry

    Science.gov (United States)

    Stowers, M. A.; van Wuijckhuijse, A. L.; Marijnissen, J. C. M.; Kientz, Ch. E.; Ciach, T.

    2006-11-01

    We have designed, constructed, and tested a system that preselects the biological fraction of airborne particles from the overall aerosol. The preselection is based on fluorescence emission excited by a continuous 266 nm laser beam. This beam is one of two cw beams used to measure the aerodynamic particle size of sampled particles. The intention in our system is that single particles, based on size and fluorescence emission, can be selected and further examined for chemical composition by mass spectrometry.

  18. Mass spectrometry based protein identification with accurate statistical significance assignment

    OpenAIRE

    Alves, Gelio; Yu, Yi-Kuo

    2014-01-01

    Motivation: Assigning statistical significance accurately has become increasingly important as meta data of many types, often assembled in hierarchies, are constructed and combined for further biological analyses. Statistical inaccuracy of meta data at any level may propagate to downstream analyses, undermining the validity of scientific conclusions thus drawn. From the perspective of mass spectrometry based proteomics, even though accurate statistics for peptide identification can now be ach...

  19. Accelerator mass spectrometry for quantitative in vivo tracing

    Energy Technology Data Exchange (ETDEWEB)

    Vogel, J S

    2005-04-19

    Accelerator mass spectrometry (AMS) counts individual rare, usually radio-, isotopes such as radiocarbon at high efficiency and specificity in milligram-sized samples. AMS traces very low chemical doses ({micro}g) and radiative doses (100 Bq) of isotope labeled compounds in animal models and directly in humans for pharmaceutical, nutritional, or toxicological research. Absorption, metabolism, distribution, binding, and elimination are all quantifiable with high precision after appropriate sample definition.

  20. Kinetic Studies of Reactions in Solution Using Fast Mass Spectrometry

    Science.gov (United States)

    2013-08-13

    REPORT Directorate of Chemistry and Materials Research NUMBER(S) AFOSR/RSA, 875 Randolph St., Suite 325, Rm 3112, Arlington, VA 222C 3 12...Mass Spectrometry to detect transient intermediates and decomposition products of catalyzed organometallic reactions Identifying intermediates is...in organometallic catalysis. HV N2 45o 5 mm 2 mm Reagent A Reagent B MS Secondary microdroplets Surface ~2-5 ms reaction time

  1. New Applications of Mass Spectrometry in Lipid Analysis*

    OpenAIRE

    Robert C. Murphy; Gaskell, Simon J

    2011-01-01

    Mass spectrometry has emerged as a powerful tool for the analysis of all lipids. Lipidomic analysis of biological systems using various approaches is now possible with a quantitative measurement of hundreds of lipid molecular species. Although availability of reference and internal standards lags behind the field, approaches using stable isotope-labeled derivative tagging permit precise determination of specific phospholipids in an experimental series. The use of reactivity of ozone has enabl...

  2. Quality management in clinical application of mass spectrometry measurement systems.

    Science.gov (United States)

    Vogeser, Michael; Seger, Christoph

    2016-09-01

    Thanks to highly specific analyte detection and potentially complete compensation for matrix variables based on the principle of stable isotope derivative internal standardisation, mass spectrometry methods allow the development of diagnostic tests of outstanding analytical quality. However, these features per se do not guarantee reliability of tests. A wide range of factors can introduce analytical errors and inaccuracy due to the extreme complexity of the methods involved. Furthermore, it can be expected that the application patterns of MS methods in diagnostic laboratories will change substantially during the coming years - with presumably less specialised laboratories implementing mass spectrometry. Introduction of highly automated test solutions by manufacturers will require some trade-off between operation convenience, sample throughput and analytical performance. Structured and careful quality and risk management is therefore crucial to translate the analytical power of mass spectrometry into actionable and reliable results for individual patients' care and to maintain the degree of reliability that is expected from MS methods in clinical pathology. This reflection review discusses whether particular quality assurance tools have to be applied for MS-based diagnostic tests and whether these tools are different from those applied for optical- and affinity-based standard tests. Both pre-implementation strategies and surveillance of assays with assessment of metadata in routine testing are addressed. The release of the CLSI guideline C62-A in 2014 was a substantial achievement in this context because it addresses a wide spectrum of relevant issues in quality assurance of mass spectrometry-based clinical tests. However, the translation of this best practice document into individual laboratory settings is likely to be heterogeneous.

  3. ESI and MALDI Mass Spectrometry of Large POSS Oligomers (Preprint)

    Science.gov (United States)

    2010-03-10

    Materials Science, 8 (2004) 21-29. [10] J. Wu and P. T. Mather, POSS Polymers: Physical Properties and Biomaterials Applications. Polym. Rev.. 49 (2009...10 (1999) 224-230. [16] M. Farahani, J. M. Antonucci and C. M. Guttman, Analysis of the interactions of a trialkoxysilane with dental monomers...Antonucci and C. M. Guttman, Analysis by mass spectrometry of the hydrolysis/condensation reaction of a trialkoxysilane in various dental monomer

  4. Sheathless interface for coupling capillary electrophoresis with mass spectrometry

    Science.gov (United States)

    Wang, Chenchen; Tang, Keqi; Smith, Richard D.

    2014-06-17

    A sheathless interface for coupling capillary electrophoresis (CE) with mass spectrometry is disclosed. The sheathless interface includes a separation capillary for performing CE separation and an emitter capillary for electrospray ionization. A portion of the emitter capillary is porous or, alternatively, is coated to form an electrically conductive surface. A section of the emitter capillary is disposed within the separation capillary, forming a joint. A metal tube, containing a conductive liquid, encloses the joint.

  5. Multidimensional Mass Spectrometry of Synthetic Polymers and Advanced Materials.

    Science.gov (United States)

    Wesdemiotis, Chrys

    2017-02-01

    Multidimensional mass spectrometry interfaces a suitable ionization technique and mass analysis (MS) with fragmentation by tandem mass spectrometry (MS(2) ) and an orthogonal online separation method. Separation choices include liquid chromatography (LC) and ion-mobility spectrometry (IMS), in which separation takes place pre-ionization in the solution state or post-ionization in the gas phase, respectively. The MS step provides elemental composition information, while MS(2) exploits differences in the bond stabilities of a polymer, yielding connectivity and sequence information. LC conditions can be tuned to separate by polarity, end-group functionality, or hydrodynamic volume, whereas IMS adds selectivity by macromolecular shape and architecture. This Minireview discusses how selected combinations of the MS, MS(2) , LC, and IMS dimensions can be applied, together with the appropriate ionization method, to determine the constituents, structures, end groups, sequences, and architectures of a wide variety of homo- and copolymeric materials, including multicomponent blends, supramolecular assemblies, novel hybrid materials, and large cross-linked or nonionizable polymers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Significant advancement of mass spectrometry imaging for food chemistry.

    Science.gov (United States)

    Yoshimura, Yukihiro; Goto-Inoue, Naoko; Moriyama, Tatsuya; Zaima, Nobuhiro

    2016-11-01

    Food contains various compounds that have an impact on our daily lives. Many technologies have been established to analyze these molecules of interest in foods. However, the analysis of the spatial distribution of these compounds in foods using conventional technology, such as high-performance liquid chromatography-mass spectrometry or gas chromatography-mass spectrometry is difficult. Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) is considered an ideal complementary approach. MALDI-MSI is a two-dimensional MALDI-MS technology that can detect compounds in a tissue section without extraction, purification, separation, or labeling. MALDI-MSI can be used to visualize the spatial distribution of chemical compounds or biomolecules in foods. Although the methodology of MALDI-MSI in food science is not yet fully established, the versatility of MALDI-MSI is expected to open a new frontier in food science. Herein, we describe the principles and applications of MALDI-MSI in food science and related fields.

  7. Differentiating Fragmentation Pathways of Cholesterol by Two-Dimensional Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    National Research Council Canada - National Science Library

    van Agthoven, Maria A; Barrow, Mark P; Chiron, Lionel; Coutouly, Marie-Aude; Kilgour, David; Wootton, Christopher A; Wei, Juan; Soulby, Andrew; Delsuc, Marc-André; Rolando, Christian; O’Connor, Peter B

    2015-01-01

    ...) Fourier transform ion cyclotron resonance mass spectrometry. In the resulting 2D mass spectrum, the fragmentation patterns of the radical and protonated species from cholesterol are differentiated...

  8. Characterization of individual particles in gaseous media by mass spectrometry

    Science.gov (United States)

    Sinha, M. P.

    1990-01-01

    An introduction is given to a system for particle analysis by mass spectrometry (PAMS) which employs particle-beam techniques to measure mass spectra on a continuous real-time basis. The system is applied to particles of both organic and inorganic compounds, and the measurements give the chemical characteristics of particles in mixtures and indicate source apportionment. The PAMS system can be used for process control and studying heterogeneous/catalytic reactions in particles, and can be fitted to study the real-time attributes of PAMS.

  9. SVSCf plasma desorption mass spectrometry: recent advances and applications

    Energy Technology Data Exchange (ETDEWEB)

    Kamensky, I.; Craig, A.G.

    1987-01-01

    SVSCf plasma desorption mass spectrometry (PDMS) as utilized in the BIO-ION instruments is described. The sensitivity of the technique is investigated for varying amounts of bovine insulin. The results show accurate mass assignment for pmole amounts of sample. Several methods, currently used for sample preparation in PDMS, are described. Spectra of the antibiotic nisin using two different sample preparation techniques show significant variation. The fragmentation pattern of reduced acetylated maltoheptaose is also presented. The initial results obtained using a new PDMS instrument equipped with variable flight path are shown. The increased resolution is illustrated using the extended flight path to measure the molecular ion region of the maltoheptaose.

  10. Tissue MALDI Mass Spectrometry Imaging (MALDI MSI) of Peptides.

    Science.gov (United States)

    Beine, Birte; Diehl, Hanna C; Meyer, Helmut E; Henkel, Corinna

    2016-01-01

    Matrix assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) is a technique to visualize molecular features of tissues based on mass detection. This chapter focuses on MALDI MSI of peptides and provides detailed operational instructions for sample preparation of cryoconserved and formalin-fixed paraffin-embedded (FFPE) tissue. Besides sample preparation we provide protocols for the MALDI measurement, tissue staining, and data analysis. On-tissue digestion and matrix application are described for two different commercially available and commonly used spraying devices: the SunCollect (SunChrom) and the ImagePrep (Bruker Daltonik GmbH).

  11. Matrix and energy effects during in-situ determination of Cu isotope ratios by ultraviolet-femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lazarov, Marina, E-mail: m.lazarov@mineralogie.uni-hannover.de; Horn, Ingo

    2015-09-01

    Copper isotope compositions in Cu-bearing metals and minerals have been measured by deep (194 nm) ultraviolet femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (UV-fsLA-MC-ICP-MS). Pure Cu-metal, brass, and several Cu-rich minerals (chalcopyrite, enargite, covellite, malachite and cuprite) have been investigated. A long-term reproducibility of better than 0.08‰ at the 95% confidence limit on the NIST SRM 976 (National Institute of Standards and Technology) Cu-metal standard has been achieved with this technique. The δ{sup 65}Cu values for all samples have been calculated by standard-sample-standard bracketing with NIST SRM 976. All analyses have been carried out using Ni as a mass discrimination monitor added by nebulization prior to entering the plasma torch. For further verification samples have been analysed by conventional solution nebulization MC-ICP-MS and the results obtained have been compared with those from UV-fsLA-MC-ICP-MS. Several potential matrix-induced molecular interferences on the mineral copper isotope ratio, such as ({sup 32}S{sup 33}S){sup +} and ({sup 32}S-{sup 16}O{sup 17}O){sup +} do not affect the Cu isotope measurements on sulfides, while hydrides, such as Zn–H or doubly-charged Sn{sup 2+} that interfere Ni isotopes can be either neglected or stripped by calculation. Matrix independent Cu-isotope measurements are sensitive to the energy density (fluence) applied onto the sample and can produce artificial shifts in the obtained δ{sup 65}Cu values which are on the order of 3‰ for Cu-metal, 0.5‰ for brass and 0.3‰ for malachite when using energy density of up to 2 J/cm{sup 2} for ablation. A positive correlation between applied energy density and the magnitude of the isotope ratio shift has been found in the energy density range from 0.2 to 1.3 J/cm{sup 2} which is below the ablation threshold for ns-laser ablation. The results demonstrate that by using appropriate low fluence it is possible

  12. Structural analyses of sucrose laurate regioisomers by mass spectrometry techniques

    DEFF Research Database (Denmark)

    Lie, Aleksander; Stensballe, Allan; Pedersen, Lars Haastrup

    2015-01-01

    6- And 6′-O-lauroyl sucrose were isolated and analyzed by matrix-assisted laser desorption/ionisation (MALDI) time-of-flight (TOF) mass spectrometry (MS), Orbitrap high-resolution (HR) MS, and electrospray-ionization (ESI) tandem mass spectrometry (MS/MS). The analyses aimed to explore.......8, respectively, and Orbitrap HRMS confirmed the mass of [M+Na]+ (m/z 547.2712). ESI-MS/MS on the precursor ion [M+Na]+ resulted in product ion mass spectra showing two high-intensity signals for each sample. 6-O-Lauroyl sucrose produced signals located at m/z 547.27 and m/z 385.21, corresponding to the 6-O......-lauroyl glucose sodium adduct ions, while the signals for 6′-O-lauroyl sucrose were located at m/z 385.22 and 367.20, respectively corresponding to the sodium adduct ions with 6-O-lauroyl fructose and 6-O-lauroyl fructosyl. The mass spectra of the two regioisomers were clearly different, and the investigation...

  13. Ambient Ionization Mass Spectrometry Measurement of Aminotransferase Activity

    Science.gov (United States)

    Yan, Xin; Li, Xin; Zhang, Chengsen; Xu, Yang; Cooks, R. Graham

    2017-06-01

    A change in enzyme activity has been used as a clinical biomarker for diagnosis and is useful in evaluating patient prognosis. Current laboratory measurements of enzyme activity involve multi-step derivatization of the reaction products followed by quantitative analysis of these derivatives. This study simplified the reaction systems by using only the target enzymatic reaction and directly detecting its product. A protocol using paper spray mass spectrometry for identifying and quantifying the reaction product has been developed. Evaluation of the activity of aspartate aminotransferase (AST) was chosen as a proof-of-principle. The volume of sample needed is greatly reduced compared with the traditional method. Paper spray has a desalting effect that avoids sprayer clogging problems seen when examining serum samples by nanoESI. This very simple method does not require sample pretreatment and additional derivatization reactions, yet it gives high quality kinetic data, excellent limits of detection (60 ppb from serum), and coefficients of variation <10% in quantitation. [Figure not available: see fulltext.

  14. Improving tritium exposure reconstructions using accelerator mass spectrometry

    Science.gov (United States)

    Hunt, J. R.; Vogel, J. S.; Knezovich, J. P.

    2010-01-01

    Direct measurement of tritium atoms by accelerator mass spectrometry (AMS) enables rapid low-activity tritium measurements from milligram-sized samples and permits greater ease of sample collection, faster throughput, and increased spatial and/or temporal resolution. Because existing methodologies for quantifying tritium have some significant limitations, the development of tritium AMS has allowed improvements in reconstructing tritium exposure concentrations from environmental measurements and provides an important additional tool in assessing the temporal and spatial distribution of chronic exposure. Tritium exposure reconstructions using AMS were previously demonstrated for a tree growing on known levels of tritiated water and for trees exposed to atmospheric releases of tritiated water vapor. In these analyses, tritium levels were measured from milligram-sized samples with sample preparation times of a few days. Hundreds of samples were analyzed within a few months of sample collection and resulted in the reconstruction of spatial and temporal exposure from tritium releases. Although the current quantification limit of tritium AMS is not adequate to determine natural environmental variations in tritium concentrations, it is expected to be sufficient for studies assessing possible health effects from chronic environmental tritium exposure. PMID:14735274

  15. Mass spectrometry in clinical chemistry: the case of newborn screening.

    Science.gov (United States)

    la Marca, Giancarlo

    2014-12-01

    Newborn screening (NBS) program is a complex and organized system consisting of family and personnel education, biochemical tests, confirmatory biochemical and genetic tests, diagnosis, therapy, and patient follow up. The program identifies treatable metabolic disorders possibly when asymptomatic by using dried blood spot (DBS). During the last 20 years tandem mass spectrometry (TMS) has become the leading technology in NBS programs demonstrating to be versatile, sensitive and specific. There is consistent evidence of benefits from NBS for many disorders detected by TMS as well as for congenital hypothyroidism, cystic fibrosis, congenital adrenal hyperplasia by immune-enzymatic methods. Real time PCR tests have more recently been proposed for the detection of some severe combined immunodeficiences (SCID) along with the use of TMS for ADA and PNP SCID; a first evaluation of their cost-benefit ratio is still ongoing. Avoiding false negative results by using specific biomarkers and reducing the false positive rate by using second tier tests, is fundamental for a successful NBS program. The fully integration of NBS and diagnostic laboratories with clinical service is crucial to have the best effectiveness in a comprehensive NBS system.

  16. Measurement of the 135Cs half-life with accelerator mass spectrometry and inductively coupled plasma mass spectrometry

    Science.gov (United States)

    MacDonald, C. M.; Cornett, R. J.; Charles, C. R. J.; Zhao, X. L.; Kieser, W. E.

    2016-01-01

    The isotope 135Cs is quoted as having a half-life of 2.3 Myr. However, there are three published values ranging from 1.8 to 3 Myr. This research reviews previous measurements and reports a new measurement of the half-life using newly developed accelerator mass spectrometry (AMS) and inductively coupled plasma mass spectrometry (ICPMS) techniques along with β and γ radiometric analysis. The half-life was determined to be (1.6 ±0.6 ) ×106 yr by AMS and (1.3 ±0.2 ) ×106 yr by ICPMS with 95% confidence. The two values agree with each other but differ from the accepted value by ˜40 % .

  17. Neuropeptide Signaling in Crustaceans Probed by Mass Spectrometry

    Science.gov (United States)

    Liang, Zhidan

    Neuropeptides are one of the most diverse classes of signaling molecules whose identities and functions are not yet fully understood. They have been implicated in the regulation of a wide range of physiological processes, including feeding-related and motivated behaviors, and also environmental adaptations. In this work, improved mass spectrometry-based analytical platforms were developed and applied to the crustacean systems to characterize signaling molecules. This dissertation begins with a review of mass spectrometry-based neuropeptide studies from both temporal- and spatial-domains. This review is then followed by several chapters detailing a few research projects related to the crustacean neuropeptidomic characterization and comparative analysis. The neuropeptidome of crayfish, Orconectes rusticus is characterized for the first time using mass spectrometry-based tools. In vivo microdialysis sampling technique offers the capability of direct sampling from extracellular space in a time-resolved manner. It is used to investigate the secreted neuropeptide and neurotransmitter content in Jonah crab, Cancer borealis, in this work. A new quantitation strategy using alternative mass spectrometry data acquisition approach is developed and applied for the first time to quantify neuropeptides. Coupling of this method with microdialysis enables the study of neuropeptide dynamics concurrent with different behaviors. Proof-of-principle experiments validating this approach have been carried out in Jonah crab, Cancer borealis to study feeding- and circadian rhythm-related neuropeptide changes using micoridialysis in a time-resolved manner. This permits a close correlation between behavioral and neurochemical changes, providing potential candidates for future validation of regulatory roles. In addition to providing spatial information, mass spectrometry imaging (MSI) technique enables the characterization of signaling molecules while preserving the temporal resolution. A

  18. Hypoxia, Radiosensitizers and high-LET radiation - Nimorazole fragmentation using mass spectrometry

    DEFF Research Database (Denmark)

    Feketeova, Linda; Bassler, Niels

    using mass spectrometry. Understanding the fragmentation of radiosensitizers is crucial in evaluating the radiosensitization potential and developing new and more effective drugs, which may improve TCP in hypoxic tumours when using ion beams such as carbon-12 along with LET-painting techniques. Method...

  19. Feasibility of nonvolatile buffers in capillary electrophoresis-electrospray ionization-mass spectrometry of proteins

    NARCIS (Netherlands)

    Eriksson, Jonas H.C.; Mol, Roelof; Somsen, Govert W.; Hinrichs, Wouter L.J.; Frijlink, Henderik W.; de Jong, Gerhardus J.

    2004-01-01

    The combination of capillary electrophoresis (CE) and electrospray ionization-mass spectrometry (ESI-MS) via a triaxial interface was studied as a potential means for the characterization of intact proteins. To evaluate the possibility to use a nonvolatile electrolyte for CE, the effect of sodium ph

  20. Real-Time Flavor Release from French Fries Using Atmospheric Pressure Chemical Ionization-Mass Spectrometry

    NARCIS (Netherlands)

    Loon, W.A.M.; Linssen, J.P.H.; Boelrijk, A.E.M.; Burgering, M.J.M.; Voragen, A.G.J.

    2005-01-01

    Flavor release from French fries was measured with atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) using both assessors (in vivo) and a mouth model system (in vitro). Several volatiles measured with APCI were identified with MS-MS. The effect of frying time, salt addition, and a

  1. Feasibility of nonvolatile buffers in capillary electrophoresis-electrospray ionization-mass spectrometry of proteins

    NARCIS (Netherlands)

    Eriksson, Jonas H.C.; Mol, Roelof; Somsen, Govert W.; Hinrichs, Wouter L.J.; Frijlink, Henderik W.; de Jong, Gerhardus J.

    2004-01-01

    The combination of capillary electrophoresis (CE) and electrospray ionization-mass spectrometry (ESI-MS) via a triaxial interface was studied as a potential means for the characterization of intact proteins. To evaluate the possibility to use a nonvolatile electrolyte for CE, the effect of sodium ph

  2. Multiresidue analysis of pesticides in straw roughage by liquid chromatography - tandem mass spectrometry

    Science.gov (United States)

    A multiresidue analytical method using a modification of the “quick, easy, cheap, effective, rugged, and safe” (QuEChERS) sample preparation approach combined with liquid chromatography–tandem mass spectrometry (LC-MS/MS) analysis was established and validated for the rapid determination of 69 pesti...

  3. Ion sampling and transport in Inductively Coupled Plasma Mass Spectrometry

    Science.gov (United States)

    Farnsworth, Paul B.; Spencer, Ross L.

    2017-08-01

    Quantitative accuracy and high sensitivity in inductively coupled plasma mass spectrometry (ICP-MS) depend on consistent and efficient extraction and transport of analyte ions from an inductively coupled plasma to a mass analyzer, where they are sorted and detected. In this review we examine the fundamental physical processes that control ion sampling and transport in ICP-MS and compare the results of theory and computerized models with experimental efforts to characterize the flow of ions through plasma mass spectrometers' vacuum interfaces. We trace the flow of ions from their generation in the plasma, into the sampling cone, through the supersonic expansion in the first vacuum stage, through the skimmer, and into the ion optics that deliver the ions to the mass analyzer. At each stage we consider idealized behavior and departures from ideal behavior that affect the performance of ICP-MS as an analytical tool.

  4. Fast characterization of cheeses by dynamic headspace-mass spectrometry.

    Science.gov (United States)

    Pérès, Christophe; Denoyer, Christian; Tournayre, Pascal; Berdagué, Jean-Louis

    2002-03-15

    This study describes a rapid method to characterize cheeses by analysis of their volatile fraction using dynamic headspace-mass spectrometry. Major factors governing the extraction and concentration of the volatile components were first studied. These components were extracted from the headspace of the cheeses in a stream of helium and concentrated on a Tenax TA trap. They were then desorbed by heating and injected directly into the source of a mass spectrometer via a short deactivated silica transfer line. The mass spectra of the mixture of volatile components were considered as fingerprints of the analyzed substances. Forward stepwise factorial discriminant analysis afforded a limited number of characteristic mass fragments that allowed a good classification of the batches of cheeses studied.

  5. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry identification of mycobacteria in routine clinical practice

    National Research Council Canada - National Science Library

    El Khéchine, Amel; Couderc, Carine; Flaudrops, Christophe; Raoult, Didier; Drancourt, Michel

    2011-01-01

    .... Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF MS) has previously been proven to effectively identify mycobacteria grown in high-concentration inocula from collections...

  6. Analysis of aromatic hydrocarbons in petroleum fractions using gas chromatography, mass spectrometry and mass fragmentrography

    Energy Technology Data Exchange (ETDEWEB)

    Kubelka, V.

    1980-01-01

    Mass spectrometry in combination with gas chrom. used to analyze hydrocarbon mixtures results in qualit. and semi-quant. data regarding composition of the analyzed mixture. Use of mass fragmentrography during chromatographic separation will allow simultaneous recording of changes in intensity of characteristic ions and thus determine the retention index, for this substance. Combining mass spectre and retention index, it is possible to identify the given subst. or limit the number of possible combinations.

  7. Elucidating rhizosphere processes by mass spectrometry - A review.

    Science.gov (United States)

    Rugova, Ariana; Puschenreiter, Markus; Koellensperger, Gunda; Hann, Stephan

    2017-03-01

    The presented review discusses state-of-the-art mass spectrometric methods, which have been developed and applied for investigation of chemical processes in the soil-root interface, the so-called rhizosphere. Rhizosphere soil's physical and chemical characteristics are to a great extent influenced by a complex mixture of compounds released from plant roots, i.e. root exudates, which have a high impact on nutrient and trace element dynamics in the soil-root interface as well as on microbial activities or soil physico-chemical characteristics. Chemical characterization as well as accurate quantification of the compounds present in the rhizosphere is a major prerequisite for a better understanding of rhizosphere processes and requires the development and application of advanced sampling procedures in combination with highly selective and sensitive analytical techniques. During the last years, targeted and non-targeted mass spectrometry-based methods have emerged and their combination with specific separation methods for various elements and compounds of a wide polarity range have been successfully applied in several studies. With this review we critically discuss the work that has been conducted within the last decade in the context of rhizosphere research and elemental or molecular mass spectrometry emphasizing different separation techniques as GC, LC and CE. Moreover, selected applications such as metal detoxification or nutrient acquisition will be discussed regarding the mass spectrometric techniques applied in studies of root exudates in plant-bacteria interactions. Additionally, a more recent isotope probing technique as novel mass spectrometry based application is highlighted. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Effective determination of the long-lived nuclide 41Ca in nuclear reactor bioshield concretes: comparison of liquid scintillation counting and accelerator mass spectrometry.

    Science.gov (United States)

    Warwick, P E; Croudace, I W; Hillegonds, D J

    2009-03-01

    The routine application of liquid scintillation counting to (41)Ca determination has been hindered by the absence of traceable calibration standards of known (41)Ca activity concentrations. The introduction of the new IRMM (41)Ca mass-spectrometric standards with sufficiently high (41)Ca activities for radiometric detection has partly overcome this although accurate measurement of stable Ca concentrations coupled with precise half-life data are still required to correct the certified (41)Ca:(40)Ca ratios to (41)Ca activity concentrations. In this study, (41)Ca efficiency versus quench curves have been produced using the IRMM standard, and their accuracy validated by comparison with theoretical calculations of (41)Ca efficiencies. Further verification of the technique was achieved through the analysis of (41)Ca in a reactor bioshield core that had been previously investigated for other radionuclide variations. Calcium-41 activity concentrations of up to 25 Bq/g were detected. Accelerator mass spectrometry (AMS) measurements of the same suite of samples showed a very good agreement, providing validation of the procedure. Calcium-41 activity concentrations declined exponentially with distance from the core of the nuclear reactor and correlated well with the predicted neutron flux.

  9. Effects of Conventional Heating on the Stability of Major Olive Oil Phenolic Compounds by Tandem Mass Spectrometry and Isotope Dilution Assay

    Directory of Open Access Journals (Sweden)

    Giovanni Sindona

    2010-12-01

    Full Text Available The quality of olive oils is sensorially tested by accurate and well established methods. It enables the classification of the pressed oils into the classes of extra virgin oil, virgin oil and lampant oil. Nonetheless, it would be convenient to have analytical methods for screening oils or supporting sensorial analysis using a reliable independent approach based on exploitation of mass spectrometric methodologies. A number of methods have been proposed to evaluate deficiencies of extra virgin olive oils resulting from inappropriate technological treatments, such as high or low temperature deodoration, and home cooking processes. The quality and nutraceutical value of extra virgin olive oil (EVOO can be related to the antioxidant property of its phenolic compounds. Olive oil is a source of at least 30 phenolic compounds, such as oleuropein, oleocanthal, hydroxytyrosol, and tyrosol, all acting as strong antioxidants, radical scavengers and NSAI-like drugs. We now report the efficacy of MRM tandem mass spectrometry, assisted by the isotope dilution assay, in the evaluation of the thermal stability of selected active principles of extra virgin olive oil.

  10. Electrospray ionization and matrix assisted laser desorption/ionization mass spectrometry: powerful analytical tools in recombinant protein chemistry

    DEFF Research Database (Denmark)

    Andersen, Jens S.; Svensson, B; Roepstorff, P

    1996-01-01

    Electrospray ionization and matrix assisted laser desorption/ionization are effective ionization methods for mass spectrometry of biomolecules. Here we describe the capabilities of these methods for peptide and protein characterization in biotechnology. An integrated analytical strategy is presen......Electrospray ionization and matrix assisted laser desorption/ionization are effective ionization methods for mass spectrometry of biomolecules. Here we describe the capabilities of these methods for peptide and protein characterization in biotechnology. An integrated analytical strategy...

  11. Study of coal structure using secondary ion mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Tingey, G.L.; Lytle, J.M.; Baer, D.R.; Thomas, M.T.

    1980-12-01

    Secondary-ion Mass Spectrometry (SIMS) is examined as a tool for studying the chemical structure of coal. SIMS has potential for analysis of coal because of the following characteristics: sensitivity to chemical structure; high sensitivity to all masses; application to solids; excellent depth resolution; and reasonable spatial resolution. SIMS spectra of solid coals show differences with respect to coal rank, the spectra of high rank coal being similar to that of graphite, and the spectra of low rank coal being similar to that of wood. Some functional group analysis is also possible using SIMS. Low rank coals show a larger peak at 15 amu indicating more methyl groups than found in the higher rank coals. Fragments with two and three carbon atoms have also been examined; much larger fragments are undoubtedly present but were not evaluated in this study. Examination of these groups, which are expected to contain valuable information on coal structure, is planned for future work. It has been observed that mineral atoms present in the coal have large secondary ion yields which complicate the interpretation of the spectra. Studies on mineral-free coals and model compounds are therefore recommended to facilitate determination of organic coal structure. In addition, mass spectrometry with much greater mass resolution will aid in distinguishing between various ion species.

  12. Mass spectrometry improvement on an high current ion implanter

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, J.G., E-mail: jgabriel@deea.isel.ipl.pt [Instituto Superior de Engenharia de Lisboa and Centro de Fisica Nuclear of the University of Lisbon, Rua Conselheiro Emidio Navarro, 1, 1959-007 Lisbon (Portugal); Alegria, F.C., E-mail: falegria@lx.it.pt [Instituto Superior Tecnico/Technical University of Lisbon and Instituto de Telecomunicacoes, Av. Rovisco Pais, 1, 1049-001 Lisbon (Portugal); Redondo, L.M., E-mail: lmredondo@deea.isel.ipl.pt [Instituto Superior de Engenharia de Lisboa and Centro de Fisica Nuclear of the University of Lisbon, Rua Conselheiro Emidio Navarro, 1, 1959-007 Lisbon (Portugal); Rocha, J., E-mail: jrocha@itn.pt [Instituto Tecnologico Nuclear, Estrada Nacional 10, 2686-953 Sacavem (Portugal); Alves, E., E-mail: ealves@itn.pt [Instituto Tecnologico Nuclear, Estrada Nacional 10, 2686-953 Sacavem (Portugal)

    2011-12-15

    The development of accurate mass spectrometry, enabling the identification of all the ions extracted from the ion source in a high current implanter is described. The spectrometry system uses two signals (x-y graphic), one proportional to the magnetic field (x-axes), taken from the high-voltage potential with an optic fiber system, and the other proportional to the beam current intensity (y-axes), taken from a beam-stop. The ion beam mass register in a mass spectrum of all the elements magnetically analyzed with the same radius and defined by a pair of analyzing slits as a function of their beam intensity is presented. The developed system uses a PC to control the displaying of the extracted beam mass spectrum, and also recording of all data acquired for posterior analysis. The operator uses a LabVIEW code that enables the interfacing between an I/O board and the ion implanter. The experimental results from an ion implantation experiment are shown.

  13. Capillary supercritical fluid chromatography-mass spectrometry (SFC-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Kalinoski, H.T.; Udseth, H.R.; Chess, E.K.; Smith, R.D.

    1986-10-01

    The physical and chemical characteristics of supercritical fluids have prompted the development of supercritical fluid chromatography (SFC) for the analysis of labile and less volatile compounds. High resolution chromatographic separations with efficiencies approaching those of gas chromatography and high speed analyses are possible in capillary SFC using pressure programming methods and narrow bore columns. Further refinement of the SFC-mass spectrometry interface (SFC-MS) provides the basis for extension to more polar fluid systems with greater solvating power and the selectivity and sensitivity of mass spectrometric detection. The use of polar modified fluids has been facilitated by advances in understanding of supercritical fluid phase behavior. Fluid mixtures have been prepared for analysis of more polar, higher molecular weight analytes, that allow mild chromatographic temperatures and allow full exploitation of selectivity offered through control of fluid pressure (i.e., density). Continuing development of the SFC-MS interface has led to designs which can be near routinely applied with fluids such as CO/sub 2/, and providing enhanced transport of truly nonvolatile compounds to the mass spectrometer ionization regions. These advances also include an SFC interface to a high resolution, dual electric magnetic sector instrument, allowing supercritical fluid solvents to be explited for on-line extraction-mass spectrometry for characterization of complex, often otherwise intractable, materials. 26 refs., 5 figs., 1 tab.

  14. Study of coal structure using secondary ion mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Tingey, G.L.; Lytle, J.M.; Baer, D.R.; Thomas, M.T.

    1980-12-01

    Secondary-ion Mass Spectrometry (SIMS) is examined as a tool for studying the chemical structure of coal. SIMS has potential for analysis of coal because of the following characteristics: sensitivity to chemical structure; high sensitivity to all masses; application to solids; excellent depth resolution; and reasonable spatial resolution. SIMS spectra of solid coals show differences with respect to coal rank, the spectra of high rank coal being similar to that of graphite, and the spectra of low rank coal being similar to that of wood. Some functional group analysis is also possible using SIMS. Low rank coals show a larger peak at 15 amu indicating more methyl groups than found in the higher rank coals. Fragments with two and three carbon atoms have also been examined; much larger fragments are undoubtedly present but were not evaluated in this study. Examination of these groups, which are expected to contain valuable information on coal structure, is planned for future work. It has been observed that mineral atoms present in the coal have large secondary ion yields which complicate the interpretation of the spectra. Studies on mineral-free coals and model compounds are therefore recommended to facilitate determination of organic coal structure. In addition, mass spectrometry with much greater mass resolution will aid in distinguishing between various ion species.

  15. Quantitative mass spectrometry of unconventional human biological matrices

    Science.gov (United States)

    Dutkiewicz, Ewelina P.; Urban, Pawel L.

    2016-10-01

    The development of sensitive and versatile mass spectrometric methodology has fuelled interest in the analysis of metabolites and drugs in unconventional biological specimens. Here, we discuss the analysis of eight human matrices-hair, nail, breath, saliva, tears, meibum, nasal mucus and skin excretions (including sweat)-by mass spectrometry (MS). The use of such specimens brings a number of advantages, the most important being non-invasive sampling, the limited risk of adulteration and the ability to obtain information that complements blood and urine tests. The most often studied matrices are hair, breath and saliva. This review primarily focuses on endogenous (e.g. potential biomarkers, hormones) and exogenous (e.g. drugs, environmental contaminants) small molecules. The majority of analytical methods used chromatographic separation prior to MS; however, such a hyphenated methodology greatly limits analytical throughput. On the other hand, the mass spectrometric methods that exclude chromatographic separation are fast but suffer from matrix interferences. To enable development of quantitative assays for unconventional matrices, it is desirable to standardize the protocols for the analysis of each specimen and create appropriate certified reference materials. Overcoming these challenges will make analysis of unconventional human biological matrices more common in a clinical setting. This article is part of the themed issue 'Quantitative mass spectrometry'.

  16. Intact MicroRNA Analysis Using High Resolution Mass Spectrometry

    Science.gov (United States)

    Kullolli, Majlinda; Knouf, Emily; Arampatzidou, Maria; Tewari, Muneesh; Pitteri, Sharon J.

    2014-01-01

    MicroRNAs (miRNAs) are small single-stranded non-coding RNAs that post-transcriptionally regulate gene expression, and play key roles in the regulation of a variety of cellular processes and in disease. New tools to analyze miRNAs will add understanding of the physiological origins and biological functions of this class of molecules. In this study, we investigate the utility of high resolution mass spectrometry for the analysis of miRNAs through proof-of-concept experiments. We demonstrate the ability of mass spectrometry to resolve and separate miRNAs and corresponding 3' variants in mixtures. The mass accuracy of the monoisotopic deprotonated peaks from various miRNAs is in the low ppm range. We compare fragmentation of miRNA by collision-induced dissociation (CID) and by higher-energy collisional dissociation (HCD) which yields similar sequence coverage from both methods but additional fragmentation by HCD versus CID. We measure the linear dynamic range, limit of detection, and limit of quantitation of miRNA loaded onto a C18 column. Lastly, we explore the use of data-dependent acquisition of MS/MS spectra of miRNA during online LC-MS and demonstrate that multiple charge states can be fragmented, yielding nearly full sequence coverage of miRNA on a chromatographic time scale. We conclude that high resolution mass spectrometry allows the separation and measurement of miRNAs in mixtures and a standard LC-MS setup can be adapted for online analysis of these molecules.

  17. Invited review article: Recent developments in isotope-ratio mass spectrometry for geochemistry and cosmochemistry.

    Science.gov (United States)

    Ireland, Trevor R

    2013-01-01

    Mass spectrometry is fundamental to measurements of isotope ratios for applications in isotope geochemistry, geochronology, and cosmochemistry. Magnetic-sector mass spectrometers are most common because these provide the best precision in isotope ratio measurements. Where the highest precision is desired, chemical separation followed by mass spectrometric analysis is carried out with gas (noble gas and stable isotope mass spectrometry), liquid (inductively coupled plasma mass spectrometry), or solid (thermal ionization mass spectrometry) samples. Developments in in situ analysis, including ion microprobes and laser ablation inductively coupled plasma mass spectrometry, have opened up issues concerning homogeneity according to domain size, and allow ever smaller amounts of material to be analyzed. While mass spectrometry is built solidly on developments in the 20th century, there are new technologies that will push the limits in terms of precision, accuracy, and sample efficiency. Developments of new instruments based on time-of-flight mass spectrometers could open up the ultimate levels of sensitivity per sample atom.

  18. Non-targeted screening for contaminants in paper and board food-contact materials using effect-directed analysis and accurate mass spectrometry.

    Science.gov (United States)

    Bengtström, Linda; Rosenmai, Anna Kjerstine; Trier, Xenia; Jensen, Lisbeth Krüger; Granby, Kit; Vinggaard, Anne Marie; Driffield, Malcolm; Højslev Petersen, Jens

    2016-06-01

    Due to large knowledge gaps in chemical composition and toxicological data for substances involved, paper and board food-contact materials (P&B FCM) have been emerging as a FCM type of particular concern for consumer safety. This study describes the development of a step-by-step strategy, including extraction, high-performance liquid chromatography (HPLC) fractionation, tentative identification of relevant substances and in vitro testing of selected tentatively identified substances. As a case study, we used two fractions from a recycled pizza box sample which exhibited aryl hydrocarbon receptor (AhR) activity. These fractions were analysed by gas chromatography (GC) and ultra-HPLC (UHPLC) coupled to quadrupole time-of-flight mass spectrometers (QTOF MS) in order tentatively to identify substances. The elemental composition was determined for peaks above a threshold, and compared with entries in a commercial mass spectral library for GC-MS (GC-EI-QTOF MS) analysis and an in-house built library of accurate masses for substances known to be used in P&B packaging for UHPLC-QTOF analysis. Of 75 tentatively identified substances, 15 were initially selected for further testing in vitro; however, only seven were commercially available and subsequently tested in vitro and quantified. Of these seven, the identities of three pigments found in printing inks were confirmed by UHPLC tandem mass spectrometry (QqQ MS/MS). Two pigments had entries in the database, meaning that a material relevant accurate mass database can provide a fast tentative identification. Pure standards of the seven tentatively identified substances were tested in vitro but could not explain a significant proportion of the AhR-response in the extract. Targeted analyses of dioxins and PCBs, both well-known AhR agonists, was performed. However, the dioxins could explain approximately 3% of the activity observed in the pizza box extract indicating that some very AhR active substance(s) still remain to be

  19. Analyzing the posttranslational modification status of Notch using mass spectrometry.

    Science.gov (United States)

    Kakuda, Shinako; Haltiwanger, Robert S

    2014-01-01

    Notch is modified by multiple types of posttranslational modifications, most of which are known to affect Notch function. The extracellular domain (ECD) is modified with N-glycosylation and at least three types of O-glycosylation (O-fucose, O-glucose, and O-GlcNAc), while the intracellular domain is hydroxylated, phosphorylated, and ubiquitinated. In order to analyze the structure and function of the O-glycans decorating the ECD, we have developed semiquantitative mass spectral methods for identifying modifications at individual sites on Notch that are generally applicable to most posttranslational modifications. Here we describe the expression and purification of Notch ECD fragments, digestion of the fragments with proteases to prepare for mass spectral analysis, and identification of peptides modified with O-glycans using mass spectrometry.

  20. MoS2/Ag nanohybrid: A novel matrix with synergistic effect for small molecule drugs analysis by negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    Science.gov (United States)

    Zhao, Yaju; Deng, Guoqing; Liu, Xiaohui; Sun, Liang; Li, Hui; Cheng, Quan; Xi, Kai; Xu, Danke

    2016-09-21

    This paper reports a facile synthesis of molybdenum disulfide nanosheets/silver nanoparticles (MoS2/Ag) hybrid and its use as an effective matrix in negative ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The nanohybrid exerts a strong synergistic effect, leading to high performance detection of small molecule analytes including amino acids, peptides, fatty acids and drugs. The enhancement of laser desorption/ionization (LDI) efficiency is largely attributed to the high surface roughness and large surface area for analyte adsorption, better dispersibility, increased thermal conductivity and enhanced UV energy absorption as compared to pure MoS2. Moreover, both Ag nanoparticles and the edge of the MoS2 layers function as deprotonation sites for proton capture, facilitating the charging process in negative ion mode and promoting formation of negative ions. As a result, the MoS2/Ag nanohybrid proves to be a highly attractive matrix in MALDI-TOF MS, with desired features such as high desorption/ionization efficiency, low fragmentation interference, high salt tolerance, and no sweet-spots for mass signal. These characteristic properties allowed for simultaneous analysis of eight different drugs and quantification of acetylsalicylic acid in the spiked human serum. This work demonstrates for the first time the fabrication and application of a novel MoS2/Ag hybrid, and provides a new platform for use in the rapid and high throughput analysis of small molecules by mass spectrometry.

  1. Proteomics by mass spectrometry: approaches, advances, and applications.

    Science.gov (United States)

    Yates, John R; Ruse, Cristian I; Nakorchevsky, Aleksey

    2009-01-01

    Mass spectrometry (MS) is the most comprehensive and versatile tool in large-scale proteomics. In this review, we dissect the overall framework of the MS experiment into its key components. We discuss the fundamentals of proteomic analyses as well as recent developments in the areas of separation methods, instrumentation, and overall experimental design. We highlight both the inherent strengths and limitations of protein MS and offer a rough guide for selecting an experimental design based on the goals of the analysis. We emphasize the versatility of the Orbitrap, a novel mass analyzer that features high resolution (up to 150,000), high mass accuracy (2-5 ppm), a mass-to-charge range of 6000, and a dynamic range greater than 10(3). High mass accuracy of the Orbitrap expands the arsenal of the data acquisition and analysis approaches compared with a low-resolution instrument. We discuss various chromatographic techniques, including multidimensional separation and ultra-performance liquid chromatography. Multidimensional protein identification technology (MudPIT) involves a continuum sample preparation, orthogonal separations, and MS and software solutions. We discuss several aspects of MudPIT applications to quantitative phosphoproteomics. MudPIT application to large-scale analysis of phosphoproteins includes (a) a fractionation procedure for motif-specific enrichment of phosphopeptides, (b) development of informatics tools for interrogation and validation of shotgun phosphopeptide data, and (c) in-depth data analysis for simultaneous determination of protein expression and phosphorylation levels, analog to western blot measurements. We illustrate MudPIT application to quantitative phosphoproteomics of the beta adrenergic pathway. We discuss several biological discoveries made via mass spectrometry pipelines with a focus on cell signaling proteomics.

  2. Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Schierbeek, H.; Houtekamer, M.; van Engeland, T.; Derrien, D.; Stal, L.J.; Boschker, H.T.S.

    2015-01-01

    We compared gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) for the measurement of d13C values in carbohydrates. Contrary to GC/IRMS, no derivatisation is needed for LC/IRMS analysis of carbohydrates. Hence, although

  3. Characterisation of the volatile profiles of infant formulas by proton transfer reaction-mass spectrometry and gas chromatography-mass spectrometry

    NARCIS (Netherlands)

    Ruth, van S.M.; Floris, V.; Fayoux, S.

    2006-01-01

    The volatile profiles of 13 infant formulas were evaluated by proton transfer reaction-mass spectrometry (PTR-MS) and gas chromatography¿mass spectrometry (GC¿MS). The infant formulas varied in brand (Aptamil, Cow & Gate, SMA), type (for different infant target groups) and physical form (powder/

  4. Atmospheric-Pressure Chemical Ionization Tandem Mass Spectrometry (APGC/MS/MS) an Alternative to High-Resolution Mass Spectrometry (HRGC/HRMS) for the Determination of Dioxins

    NARCIS (Netherlands)

    Bavel, Van Bert; Geng, Dawei; Cherta, Laura; Nácher-Mestre, Jaime; Portolés, Tania; Ábalos, Manuela; Sauló, Jordi; Abad, Esteban; Dunstan, Jody; Jones, Rhys; Kotz, Alexander; Winterhalter, Helmut; Malisch, Rainer; Traag, Wim; Hagberg, Jessika; Ericson Jogsten, Ingrid; Beltran, Joaquim; Hernández, Félix

    2015-01-01

    The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of usin

  5. Identification of Fatty Acids, Phospholipids, and Their Oxidation Products Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry and Electrospray Ionization Mass Spectrometry

    Science.gov (United States)

    Harmon, Christopher W.; Mang, Stephen A.; Greaves, John; Finlayson-Pitts, Barbara J.

    2010-01-01

    Electrospray ionization mass spectrometry (ESI-MS) and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) have found increasing application in the analysis of biological samples. Using these techniques to solve problems in analytical chemistry should be an essential component of the training of undergraduate chemists. We…

  6. Identification of Fatty Acids, Phospholipids, and Their Oxidation Products Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry and Electrospray Ionization Mass Spectrometry

    Science.gov (United States)

    Harmon, Christopher W.; Mang, Stephen A.; Greaves, John; Finlayson-Pitts, Barbara J.

    2010-01-01

    Electrospray ionization mass spectrometry (ESI-MS) and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) have found increasing application in the analysis of biological samples. Using these techniques to solve problems in analytical chemistry should be an essential component of the training of undergraduate chemists. We…

  7. Secondary electrospray ionization ion mobility spectrometry/mass spectrometry of illicit drugs.

    Science.gov (United States)

    Wu, C; Siems, W F; Hill, H H

    2000-01-15

    A secondary electrospray ionization (SESI) method was developed as a nonradioactive ionization source for ion mobility spectrometry (IMS). This SESI method relied on the gas-phase interaction between charged particles created by electrospray ionization (ESI) and neutral gaseous sample molecules. Mass spectrometry (MS) was used as the detection method after ion mobility separation for ion identification. Preliminary investigations focussed on understanding the ionization process of SESI. The performance of ESI-IMS and SESI-IMS for illicit drug detection was evaluated by determining the analytical figures of merit. In general, SESI had a higher ionization efficiency for small volatile molecules compared with the electrospray method. The potential of developing a universal interface for both GC- and LC-MS with an addition stage of mobility separation was demonstrated.

  8. Uncovering biologically significant lipid isomers with liquid chromatography, ion mobility spectrometry and mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kyle, Jennifer E.; Zhang, Xing; Weitz, Karl K.; Monroe, Matthew E.; Ibrahim, Yehia M.; Moore, Ronald J.; Cha, Jeeyeon; Sun, Xiaofei; Lovelace, Erica S.; Wagoner, Jessica; Polyak, Steve; Metz, Thomas O.; Dey, Sudhansu K.; Smith, Richard D.; Burnum-Johnson, Kristin E.; Baker, Erin Shammel

    2016-01-01

    Understanding how biological molecules are generated, metabolized and eliminated in living systems is important for interpreting processes such as immune response and disease pathology. While genomic and proteomic studies have provided vast amounts of information over the last several decades, interest in lipidomics has also grown due to improved analytical technologies revealing altered lipid metabolism in type 2 diabetes, cancer, and lipid storage disease. Liquid chromatography and mass spectrometry (LC-MS) measurements are currently the dominant approach for characterizing the lipidome by providing detailed information on the spatial and temporal composition of lipids. However, interpreting lipids’ biological roles is challenging due to the existence of numerous structural and stereoisomers (i.e. distinct acyl chain and double-bond positions), which are unresolvable using present LC-MS approaches. Here we show that combining structurally-based ion mobility spectrometry (IMS) with LC-MS measurements distinguishes lipid isomers and allows insight into biological and disease processes.

  9. Rapid Analysis of Isobaric Exogenous Metabolites by Differential Mobility Spectrometry Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Parson, Whitney B [ORNL; Schneider, Bradley B [MDS Sciex; Kertesz, Vilmos [ORNL; Corr, Jay [AB Sciex; Covey, Thomas R. [MDS Sciex; Van Berkel, Gary J [ORNL

    2011-01-01

    The direct separation of isobaric glucuronide metabolites from propranolol dosed tissue extracts by differential mobility spectrometry mass spectrometry (DMS-MS) with the use of a polar gas-phase chemical modifier was demonstrated. The DMS gas-phase separation was able to resolve the isobaric metabolites with separation times on the order of ms instead of mins to hrs typically required when using pre-ionization chromatographic separation methods. Direct separation of isobaric metabolites from the complex tissue extract was validated using standards as well as implementing an HPLC separation prior to the DMS-MS analysis to pre-separate the species of interest. The ability to separate isobaric exogenous metabolites directly from a complex tissue extract is expected to facilitate the drug development process by increasing analytical throughput without the requirement for pre-ionization cleanup or separation strategies.

  10. Direct and Convenient Mass Spectrometry Sampling with Ambient Flame Ionization

    Science.gov (United States)

    Liu, Xiao-Pan; Wang, Hao-Yang; Zhang, Jun-Ting; Wu, Meng-Xi; Qi, Wan-Shu; Zhu, Hui; Guo, Yin-Long

    2015-11-01

    Recent innovations in ambient ionization technology for the direct analysis of various samples in their native environment facilitate the development and applications of mass spectrometry in natural science. Presented here is a novel, convenient and flame-based ambient ionization method for mass spectrometric analysis of organic compounds, termed as the ambient flame ionization (AFI) ion source. The key features of AFI ion source were no requirement of (high) voltages, laser beams and spray gases, but just using small size of n-butane flame (height approximately 1 cm, about 500 oC) to accomplish the rapid desorption and ionization for direct analysis of gaseous-, liquid- and solid-phase organic compounds, as well as real-world samples. This method has high sensitivity with a limit of detection of 1 picogram for propyphenazone, which allows consuming trace amount of samples. Compared to previous ionization methods, this ion source device is extremely simple, maintain-free, low-cost, user-friendly so that even an ordinary lighter (with n-butane as fuel) can achieve efficient ionization. A new orientation to mass spectrometry ion source exploitation might emerge from such a convenient, easy and inexpensive AFI ion source.

  11. Mass Spectrometry Based Lipidomics: An Overview of Technological Platforms

    Directory of Open Access Journals (Sweden)

    Harald C. Köfeler

    2012-01-01

    Full Text Available One decade after the genomic and the proteomic life science revolution, new ‘omics’ fields are emerging. The metabolome encompasses the entity of small molecules—Most often end products of a catalytic process regulated by genes and proteins—with the lipidome being its fat soluble subdivision. Within recent years, lipids are more and more regarded not only as energy storage compounds but also as interactive players in various cellular regulation cycles and thus attain rising interest in the bio-medical community. The field of lipidomics is, on one hand, fuelled by analytical technology advances, particularly mass spectrometry and chromatography, but on the other hand new biological questions also drive analytical technology developments. Compared to fairly standardized genomic or proteomic high-throughput protocols, the high degree of molecular heterogeneity adds a special analytical challenge to lipidomic analysis. In this review, we will take a closer look at various mass spectrometric platforms for lipidomic analysis. We will focus on the advantages and limitations of various experimental setups like ‘shotgun lipidomics’, liquid chromatography—Mass spectrometry (LC-MS and matrix assisted laser desorption ionization-time of flight (MALDI-TOF based approaches. We will also examine available software packages for data analysis, which nowadays is in fact the rate limiting step for most ‘omics’ workflows.

  12. Rapid analysis of trace pollutants using laser mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Organic pollution has been gaining more and more attention.Yet,at present the determination of virtually all of them,including polycyclic aromatic carbons (PAHs),the largest single class of chemical carcinogens known today,is made via pre-purification and pre-concentration.The major problems are complexity and time-consuming,thus,no ideal real-time on-line monitoring can be done.Laser mass spectrometry combines UV spectroscopy and time-of-flight mass spectrometry (TOF-MS) through resonance-enhanced multiphoton ionization (REMPI).It is characteristic of high sensitivity,high selectivity and rapidity.In this paper,after its principles,a small mobile laser mass spectrometer,in which a mini-excimer (KrF,248 nm) laser was used,is introduced.Real-time analysis of vehicle exhaust gas was made using this instrument,and the results showed some advantages over traditional methods:multicomponent detection,including benzene,toluene,xylene,C3-benzene,naphthalene,and methyl-naphthalene; high sensitivity (100 ppb);high time-resolution (0.1 s);and no need for pre-purification or pre-concentration of samples.

  13. Overview of mass spectrometry-based metabolomics: opportunities and challenges.

    Science.gov (United States)

    Gowda, G A Nagana; Djukovic, Danijel

    2014-01-01

    The field of metabolomics has witnessed an exponential growth in the last decade driven by important applications spanning a wide range of areas in the basic and life sciences and beyond. Mass spectrometry in combination with chromatography and nuclear magnetic resonance are the two major analytical avenues for the analysis of metabolic species in complex biological mixtures. Owing to its inherent significantly higher sensitivity and fast data acquisition, MS plays an increasingly dominant role in the metabolomics field. Propelled by the need to develop simple methods to diagnose and manage the numerous and widespread human diseases, mass spectrometry has witnessed tremendous growth with advances in instrumentation, experimental methods, software, and databases. In response, the metabolomics field has moved far beyond qualitative methods and simple pattern recognition approaches to a range of global and targeted quantitative approaches that are now routinely used and provide reliable data, which instill greater confidence in the derived inferences. Powerful isotope labeling and tracing methods have become very popular. The newly emerging ambient ionization techniques such as desorption ionization and rapid evaporative ionization have allowed direct MS analysis in real time, as well as new MS imaging approaches. While the MS-based metabolomics has provided insights into metabolic pathways and fluxes, and metabolite biomarkers associated with numerous diseases, the increasing realization of the extremely high complexity of biological mixtures underscores numerous challenges including unknown metabolite identification, biomarker validation, and interlaboratory reproducibility that need to be dealt with for realization of the full potential of MS-based metabolomics. This chapter provides a glimpse at the current status of the mass spectrometry-based metabolomics field highlighting the opportunities and challenges.

  14. Evaluation of treadmill exercise effect on muscular lipid profiles of diabetic fatty rats by nanoflow liquid chromatography-tandem mass spectrometry

    Science.gov (United States)

    Lee, Jong Cheol; Kim, Il Yong; Son, Yeri; Byeon, Seul Kee; Yoon, Dong Hyun; Son, Jun Seok; Song, Han Sol; Song, Wook; Seong, Je Kyung; Moon, Myeong Hee

    2016-07-01

    We compare comprehensive quantitative profiling of lipids at the molecular level from skeletal muscle tissues (gastrocnemius and soleus) of Zucker diabetic fatty rats and Zucker lean control rats during treadmill exercise by nanoflow liquid chromatography-tandem mass spectrometry. Because type II diabetes is caused by decreased insulin sensitivity due to excess lipids accumulated in skeletal muscle tissue, lipidomic analysis of muscle tissues under treadmill exercise can help unveil the mechanism of lipid-associated insulin resistance. In total, 314 lipid species, including phospholipids, sphingolipids, ceramides, diacylglycerols (DAGs), and triacylglycerols (TAGs), were analyzed to examine diabetes-related lipid species and responses to treadmill exercise. Most lysophospholipid levels increased with diabetes. While DAG levels (10 from the gastrocnemius and 13 from the soleus) were >3-fold higher in diabetic rats, levels of most of these decreased after exercise in soleus but not in gastrocnemius. Levels of 5 highly abundant TAGs (52:1 and 54:3 in the gastrocnemius and 48:2, 50:2, and 52:4 in the soleus) displaying 2-fold increases in diabetic rats decreased after exercise in the soleus but not in the gastrocnemius in most cases. Thus, aerobic exercise has a stronger influence on lipid levels in the soleus than in the gastrocnemius in type 2 diabetic rats.

  15. Evaluation of selected-ion flow-tube mass spectrometry for the measurement of ethanol, methanol and isopropanol in physiological fluids: effect of osmolality and sample volume.

    Science.gov (United States)

    Rowbottom, Lynn; Workman, Clive; Roberts, Norman B

    2009-09-01

    Selected-ion flow-tube mass spectrometry (SIFT-MS) is particularly suited for the analysis of volatile low molecular weight compounds. We have evaluated this technique for the assay of different alcohols in aqueous solutions, including blood plasma, and in particular whether the osmolality or sample volume affected vapourisation. Solutions of three different alcohols (methanol, ethanol and isopropanol) ranging from 0.005 to 50 mmol/L were prepared in deionised water (0 milliosmol), phosphate-buffered saline (690 mOsm), isotonic saline (294 mOsm) and plasma (296 mOsm). The vapour above the sample (50 to 1000 microL) contained in air-tight tubes at 37 degrees C was aspirated into the instrument. The outputs for ethanol, methanol and isopropanol were linear over the concentration range and independent of the sample volume and relatively independent of the osmolar concentration. SIFT-MS can reliably and accurately measure common alcohols in the headspace above aqueous solutions, including serum/plasma. This novel application of SIFT-MS is easy to follow, requires no sample preparation and the wide dynamic range will facilitate measurement of alcohols present from normal metabolism as well as when taken in excess or in accidental poisoning.

  16. Effective Ion Mobility Peak Width as a New Isomeric Descriptor for the Untargeted Analysis of Complex Mixtures Using Ion Mobility-Mass Spectrometry

    Science.gov (United States)

    Farenc, Mathilde; Paupy, Benoit; Marceau, Sabrina; Riches, Eleanor; Afonso, Carlos; Giusti, Pierre

    2017-07-01

    Ion mobility coupled with mass spectrometry was proven to be an efficient way to characterize complex mixtures such as petroleum samples. However, the identification of isomeric species is difficult owing to the molecular complexity of petroleum and no availability of standard molecules. This paper proposes a new simple indicator to estimate the isomeric content of highly complex mixtures. This indicator is based on the full width at half maximum (FWHM) of the extracted ion mobility peak measured in millisecond or square angstrom that is corrected for instrumental factors such as ion diffusion. This value can be easily obtained without precisely identifying the number of isomeric species under the ion mobility peaks. Considering the Boduszynski model, the ion mobility profile for a particular elemental composition is expected to be a continuum of various isomeric species. The drift time-dependent fragmentation profile was studied and confirmed this hypothesis, a continuous evolution of the fragmentation profile showing that the larger alkyl chain species were detected at higher drift time values. This new indicator was proven to be a fast and efficient method to compare vacuum gas oils for which no difference was found using other analytical techniques.

  17. The effect of co-occurring polychlorinated biphenyls on quantitation of toxaphene in fish tissue samples by gas chromatography negative ion mass spectrometry.

    Science.gov (United States)

    Lao, Wenjian; Tsukada, David; Maruya, Keith A

    2012-12-28

    Determinative methods based on gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS) provide improved sensitivity and specificity for toxaphene in environmental samples, but are subject to misidentification due to oxygen reaction in the presence of polychlorinated biphenyls (PCBs). The goal of this study was to quantify the impact of co-occurring PCBs in fish tissue samples when utilizing single quadrupole instruments to implement this method. Mixtures of PCB congeners and technical toxaphene, and extracts of fish tissue with varying concentrations of PCBs were analyzed for individual congener and total toxaphene concentrations by GC-NCI/MS. The contribution of co-injected PCB 204 ranged from 23% to 88% of the total peak area for the Cl-9 toxaphene homolog quantitation ion, a contribution that increased as the ratio of technical toxaphene to PCB 204 decreased. PCB interferences in fish tissue extracts, including a standard reference material, were subtracted using a three-step procedure featuring spectral analysis of isotopic patterns for target peaks. Total toxaphene concentrations without PCB subtraction in three fish tissue samples with low, intermediate and high co-occurring PCBs were overestimated by 33, 55 and 745%, respectively, underscoring the need for practical strategies to account for PCB interferences in GC-NCI/MS based protocols. In contrast, no appreciable interference or resulting positive bias in concentrations was observed for quantitation of eight common toxaphene residue congeners.

  18. Small sample Accelerator Mass Spectrometry for biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    Salehpour, M., E-mail: mehran.salehpour@physics.uu.se; Håkansson, K.; Possnert, G.

    2015-10-15

    The Accelerator Mass Spectrometry activities at Uppsala University include a group dedicated to the biomedical applications, involving natural level samples, as well as {sup 14}C-labeled substances requiring separate handling and preparation. For most applications sufficient sample amounts are available but many applications are limited to samples sizes in the μg-range. We have developed a preparation procedure for small samples biomedical applications, where a few μg C can be analyzed, albeit with compromised precision. The latest results for the small sample AMS method are shown and some of the biomedical activities at our laboratory are presented.

  19. Mass spectrometry cancer data classification using wavelets and genetic algorithm.

    Science.gov (United States)

    Nguyen, Thanh; Nahavandi, Saeid; Creighton, Douglas; Khosravi, Abbas

    2015-12-21

    This paper introduces a hybrid feature extraction method applied to mass spectrometry (MS) data for cancer classification. Haar wavelets are employed to transform MS data into orthogonal wavelet coefficients. The most prominent discriminant wavelets are then selected by genetic algorithm (GA) to form feature sets. The combination of wavelets and GA yields highly distinct feature sets that serve as inputs to classification algorithms. Experimental results show the robustness and significant dominance of the wavelet-GA against competitive methods. The proposed method therefore can be applied to cancer classification models that are useful as real clinical decision support systems for medical practitioners.

  20. Monitoring of wine aging process by electrospray ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    Alexandra Christine Helena Frankland Sawaya

    2011-09-01

    Full Text Available The characterization of wine samples by direct insertion electrospray ionization mass spectrometry (ESI-MS, without pre-treatment or chromatographic separation, in a process denominated fingerprinting, has been applied to several samples of wine produced with grapes of the Pinot noir, Merlot and Cabernet Sauvignon varieties from the state o Rio Grande do Sul, in Brazil. The ESI-MS fingerprints of the samples detected changes which occurred during the aging process in the three grape varieties. Principal Component Analysis (PCA of the negative ion mode fingerprints was used to group the samples, pinpoint the main changes in their composition, and indicate marker ions for each group of samples.

  1. Temperature-programmed desorption for membrane inlet mass spectrometry

    DEFF Research Database (Denmark)

    Ketola, R.A.; Grøn, C.; Lauritsen, F.R.

    1998-01-01

    We present a novel technique for analyzing volatile organic compounds in air samples using a solid adsorbent together with temperature-programmed desorption and subsequent detection by membrane inlet mass spectrometry (TPD-MIMS). The new system has the advantage of a fast separation of compounds...... prior to the detection by MIMS. The gaseous sample is simply adsorbed on the adsorbent, which is then rapidly heated from 30 degrees C to 250 degrees C at a rate of 50 degrees C/min, Trapped organic compounds are released from the adsorbent into a helium stream at different temperatures depending...

  2. Optimizing the identification of citrullinated peptides by mass spectrometry

    DEFF Research Database (Denmark)

    Bennike, Tue; Lauridsen, Kasper B.; Olesen, Michael Kruse

    2013-01-01

    using digested synovial fluid samples from a rheumatoid arthritis patient. The samples were analyzed using liquid chromatography/tandem MS with electrospray ionization. Our in vivo and in vitro studies clearly demonstrate the inability of trypsin to cleave after citrulline residues. Based on our......Citrullinated proteins have been associated with several diseases and citrullination can most likely function as a target for novel diagnostic agents and unravel disease etiologies. The correct identification of citrullinated proteins is therefore of most importance. Mass spectrometry (MS) driven...

  3. Solid support resins and affinity purification mass spectrometry.

    Science.gov (United States)

    Havis, Spencer; Moree, Wilna J; Mali, Sujina; Bark, Steven J

    2017-02-28

    Co-affinity purification-mass spectrometry (CoAP-MS) is a primary technology for elucidating the protein-protein interactions that form the basis of all biological processes. A critical component of CoAP-MS is the affinity purification (AP) of the bait protein, usually by immobilization of an antibody to a solid-phase resin. This Minireview discusses common resins, reagents, tagging methods, and their consideration for successful AP of tagged proteins. We discuss our experiences with different solid supports, their impact in AP experiments, and propose areas where chemistry can advance this important technology.

  4. Applications of ambient mass spectrometry in high-throughput screening.

    Science.gov (United States)

    Li, Li-Ping; Feng, Bao-Sheng; Yang, Jian-Wang; Chang, Cui-Lan; Bai, Yu; Liu, Hu-Wei

    2013-06-07

    The development of rapid screening and identification techniques is of great importance for drug discovery, doping control, forensic identification, food safety and quality control. Ambient mass spectrometry (AMS) allows rapid and direct analysis of various samples in open air with little sample preparation. Recently, its applications in high-throughput screening have been in rapid progress. During the past decade, various ambient ionization techniques have been developed and applied in high-throughput screening. This review discusses typical applications of AMS, including DESI (desorption electrospray ionization), DART (direct analysis in real time), EESI (extractive electrospray ionization), etc., in high-throughput screening (HTS).

  5. Vaporization Studies of Olivine via Knudsen Effusion Mass Spectrometry

    Science.gov (United States)

    Costa, G. C. C.; Jacobson, N. S.

    2014-01-01

    Olivine is the major mineral in the Earth's upper mantle occurring predominantly in igneous rocks and has been identified in meteorites, asteroids, the Moon and Mars. Among many other important applications in planetary and materials sciences, the thermodynamic properties of vapor species from olivine are crucial as input parameters in computational modelling of the atmospheres of hot, rocky exoplanets (lava planets). There are several weight loss studies of olivine vaporization in the literature and one Knudsen Effusion Mass Spectrometry (KEMS) study. In this study, we examine a forsterite-rich olivine (93% forsterite and 7% fayalite, Fo93Fa7) with KEMS to further understand its vaporization and thermodynamic properties.

  6. Clusters of Monoisotopic Elements for Calibration in (TOF) Mass Spectrometry

    Science.gov (United States)

    Kolářová, Lenka; Prokeš, Lubomír; Kučera, Lukáš; Hampl, Aleš; Peňa-Méndez, Eladia; Vaňhara, Petr; Havel, Josef

    2016-12-01

    Precise calibration in TOF MS requires suitable and reliable standards, which are not always available for high masses. We evaluated inorganic clusters of the monoisotopic elements gold and phosphorus (Au n +/Au n - and P n +/P n -) as an alternative to peptides or proteins for the external and internal calibration of mass spectra in various experimental and instrumental scenarios. Monoisotopic gold or phosphorus clusters can be easily generated in situ from suitable precursors by laser desorption/ionization (LDI) or matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Their use offers numerous advantages, including simplicity of preparation, biological inertness, and exact mass determination even at lower mass resolution. We used citrate-stabilized gold nanoparticles to generate gold calibration clusters, and red phosphorus powder to generate phosphorus clusters. Both elements can be added to samples to perform internal calibration up to mass-to-charge (m/z) 10-15,000 without significantly interfering with the analyte. We demonstrated the use of the gold and phosphorous clusters in the MS analysis of complex biological samples, including microbial standards and total extracts of mouse embryonic fibroblasts. We believe that clusters of monoisotopic elements could be used as generally applicable calibrants for complex biological samples.

  7. Mass spectrometry of solid samples in open air using combined laser ionization and ambient metastable ionization

    Science.gov (United States)

    He, X. N.; Xie, Z. Q.; Gao, Y.; Hu, W.; Guo, L. B.; Jiang, L.; Lu, Y. F.

    2012-01-01

    Mass spectrometry of solid samples in open air was carried out using combined laser ionization and metastable ionization time-of-flight mass spectrometry (LI-MI-TOFMS) in ambient environment for qualitative and semiquantitative (relative analyte information, not absolute information) analysis. Ambient metastable ionization using a direct analysis in realtime (DART) ion source was combined with laser ionization time-of-flight mass spectrometry (LI-TOFMS) to study the effects of combining metastable and laser ionization. A series of metallic samples from the National Institute of Standards and Technology (NIST 494, 495, 498, 499, and 500) and a pure carbon target were characterized using LI-TOFMS in open air. LI-MI-TOFMS was found to be superior to laser-induced breakdown spectroscopy (LIBS). Laser pulse energies between 10 and 200 mJ at the second harmonic (532 nm) of an Nd:YAG laser were applied in the experiment to obtain a high degree of ionization in plasmas. Higher laser pulse energy improves signal intensities of trace elements (such as Fe, Cr, Mn, Ni, Ca, Al, and Ag). Data were analyzed by numerically calculating relative sensitivity coefficients (RSCs) and limit of detections (LODs) from mass spectrometry (MS) and LIBS spectra. Different parameters, such as boiling point, ionization potential, RSC, LOD, and atomic weight, were shown to analyze the ionization and MS detection processes in open air.

  8. New Developments in Liquid Chromatography Mass Spectrometry for the Determination of Micropollutants

    Directory of Open Access Journals (Sweden)

    Zoraida Sosa-Ferrera

    2012-01-01

    Full Text Available The combination of liquid chromatography (LC with mass spectrometry (MS in the environmental field has appeared as a valuable tool for the determination of micropollutants. Several groups of compounds have been considered as particularly relevant (e.g., pharmaceuticals, hormones and other endocrine-disrupting, personal care products and their metabolites, flame retardants, surfactants, and plasticizers, among others since the same ones are continuously being released in the environment mainly as a result of the manufacturing processes, the disposal of unused or expired products, and the excreta. Because these micropollutants are not completely removed in the environment, very specific and sensitive analytical procedures are needed for their identification and quantification. High performance liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS (or LC-MS2 and especially time-of-flight mass spectrometry (TOF/MS, has allowed that many environmental contaminants that are highly polar or nonvolatile or have a high molecular weight to be analyzed or identified. In this work we present an overview focused on the developments of liquid chromatography mass spectrometry applied to the analysis of the main classes of micropollutants in aqueous and solid environmental samples. Various aspects of methodologies based on these techniques, including sample preparation (extraction/preconcentration and matrix effects, are discussed.

  9. Tandem mass spectrometry data quality assessment by self-convolution

    Directory of Open Access Journals (Sweden)

    Tham Wai

    2007-09-01

    Full Text Available Abstract Background Many algorithms have been developed for deciphering the tandem mass spectrometry (MS data sets. They can be essentially clustered into two classes. The first performs searches on theoretical mass spectrum database, while the second based itself on de novo sequencing from raw mass spectrometry data. It was noted that the quality of mass spectra affects significantly the protein identification processes in both instances. This prompted the authors to explore ways to measure the quality of MS data sets before subjecting them to the protein identification algorithms, thus allowing for more meaningful searches and increased confidence level of proteins identified. Results The proposed method measures the qualities of MS data sets based on the symmetric property of b- and y-ion peaks present in a MS spectrum. Self-convolution on MS data and its time-reversal copy was employed. Due to the symmetric nature of b-ions and y-ions peaks, the self-convolution result of a good spectrum would produce a highest mid point intensity peak. To reduce processing time, self-convolution was achieved using Fast Fourier Transform and its inverse transform, followed by the removal of the "DC" (Direct Current component and the normalisation of the data set. The quality score was defined as the ratio of the intensity at the mid point to the remaining peaks of the convolution result. The method was validated using both theoretical mass spectra, with various permutations, and several real MS data sets. The results were encouraging, revealing a high percentage of positive prediction rates for spectra with good quality scores. Conclusion We have demonstrated in this work a method for determining the quality of tandem MS data set. By pre-determining the quality of tandem MS data before subjecting them to protein identification algorithms, spurious protein predictions due to poor tandem MS data are avoided, giving scientists greater confidence in the

  10. Distance-of-Flight Mass Spectrometry: What, Why, and How?

    Science.gov (United States)

    Dennis, Elise A.; Gundlach-Graham, Alexander W.; Ray, Steven J.; Enke, Christie G.; Hieftje, Gary M.

    2016-11-01

    Distance-of-flight mass spectrometry (DOFMS) separates ions of different mass-to-charge ( m/ z) by the distance they travel in a given time after acceleration. Like time-of-flight mass spectrometry (TOFMS), separation and mass assignment are based on ion velocity. However, DOFMS is not a variant of TOFMS; different methods of ion focusing and detection are used. In DOFMS, ions are driven orthogonally, at the detection time, onto an array of detectors parallel to the flight path. Through the independent detection of each m/ z, DOFMS can provide both wider dynamic range and increased throughput for m/ z of interest compared with conventional TOFMS. The iso-mass focusing and detection of ions is achieved by constant-momentum acceleration (CMA) and a linear-field ion mirror. Improved energy focus (including turn-around) is achieved in DOFMS, but the initial spatial dispersion of ions remains unchanged upon detection. Therefore, the point-source nature of surface ionization techniques could put them at an advantage for DOFMS. To date, three types of position-sensitive detectors have been used for DOFMS: a microchannel plate with a phosphorescent screen, a focal plane camera, and an IonCCD array; advances in detector technology will likely improve DOFMS figures-of-merit. In addition, the combination of CMA with TOF detection has provided improved resolution and duty factor over a narrow m/ z range (compared with conventional, single-pass TOFMS). The unique characteristics of DOFMS can enable the intact collection of large biomolecules, clusters, and organisms. DOFMS might also play a key role in achieving the long-sought goal of simultaneous MS/MS.

  11. Distance-of-Flight Mass Spectrometry: What, Why, and How?

    Science.gov (United States)

    Dennis, Elise A.; Gundlach-Graham, Alexander W.; Ray, Steven J.; Enke, Christie G.; Hieftje, Gary M.

    2016-08-01

    Distance-of-flight mass spectrometry (DOFMS) separates ions of different mass-to-charge (m/z) by the distance they travel in a given time after acceleration. Like time-of-flight mass spectrometry (TOFMS), separation and mass assignment are based on ion velocity. However, DOFMS is not a variant of TOFMS; different methods of ion focusing and detection are used. In DOFMS, ions are driven orthogonally, at the detection time, onto an array of detectors parallel to the flight path. Through the independent detection of each m/z, DOFMS can provide both wider dynamic range and increased throughput for m/z of interest compared with conventional TOFMS. The iso-mass focusing and detection of ions is achieved by constant-momentum acceleration (CMA) and a linear-field ion mirror. Improved energy focus (including turn-around) is achieved in DOFMS, but the initial spatial dispersion of ions remains unchanged upon detection. Therefore, the point-source nature of surface ionization techniques could put them at an advantage for DOFMS. To date, three types of position-sensitive detectors have been used for DOFMS: a microchannel plate with a phosphorescent screen, a focal plane camera, and an IonCCD array; advances in detector technology will likely improve DOFMS figures-of-merit. In addition, the combination of CMA with TOF detection has provided improved resolution and duty factor over a narrow m/z range (compared with conventional, single-pass TOFMS). The unique characteristics of DOFMS can enable the intact collection of large biomolecules, clusters, and organisms. DOFMS might also play a key role in achieving the long-sought goal of simultaneous MS/MS.

  12. Distance-of-Flight Mass Spectrometry: What, Why, and How?

    Science.gov (United States)

    Dennis, Elise A; Gundlach-Graham, Alexander W; Ray, Steven J; Enke, Christie G; Hieftje, Gary M

    2016-11-01

    Distance-of-flight mass spectrometry (DOFMS) separates ions of different mass-to-charge (m/z) by the distance they travel in a given time after acceleration. Like time-of-flight mass spectrometry (TOFMS), separation and mass assignment are based on ion velocity. However, DOFMS is not a variant of TOFMS; different methods of ion focusing and detection are used. In DOFMS, ions are driven orthogonally, at the detection time, onto an array of detectors parallel to the flight path. Through the independent detection of each m/z, DOFMS can provide both wider dynamic range and increased throughput for m/z of interest compared with conventional TOFMS. The iso-mass focusing and detection of ions is achieved by constant-momentum acceleration (CMA) and a linear-field ion mirror. Improved energy focus (including turn-around) is achieved in DOFMS, but the initial spatial dispersion of ions remains unchanged upon detection. Therefore, the point-source nature of surface ionization techniques could put them at an advantage for DOFMS. To date, three types of position-sensitive detectors have been used for DOFMS: a microchannel plate with a phosphorescent screen, a focal plane camera, and an IonCCD array; advances in detector technology will likely improve DOFMS figures-of-merit. In addition, the combination of CMA with TOF detection has provided improved resolution and duty factor over a narrow m/z range (compared with conventional, single-pass TOFMS). The unique characteristics of DOFMS can enable the intact collection of large biomolecules, clusters, and organisms. DOFMS might also play a key role in achieving the long-sought goal of simultaneous MS/MS. Graphical Abstract ᅟ.

  13. Global surveillance of emerging Influenza virus genotypes by mass spectrometry.

    Directory of Open Access Journals (Sweden)

    Rangarajan Sampath

    Full Text Available BACKGROUND: Effective influenza surveillance requires new methods capable of rapid and inexpensive genomic analysis of evolving viral species for pandemic preparedness, to understand the evolution of circulating viral species, and for vaccine strain selection. We have developed one such approach based on previously described broad-range reverse transcription PCR/electrospray ionization mass spectrometry (RT-PCR/ESI-MS technology. METHODS AND PRINCIPAL FINDINGS: Analysis of base compositions of RT-PCR amplicons from influenza core gene segments (PB1, PB2, PA, M, NS, NP are used to provide sub-species identification and infer influenza virus H and N subtypes. Using this approach, we detected and correctly identified 92 mammalian and avian influenza isolates, representing 30 different H and N types, including 29 avian H5N1 isolates. Further, direct analysis of 656 human clinical respiratory specimens collected over a seven-year period (1999-2006 showed correct identification of the viral species and subtypes with >97% sensitivity and specificity. Base composition derived clusters inferred from this analysis showed 100% concordance to previously established clades. Ongoing surveillance of samples from the recent influenza virus seasons (2005-2006 showed evidence for emergence and establishment of new genotypes of circulating H3N2 strains worldwide. Mixed viral quasispecies were found in approximately 1% of these recent samples providing a view into viral evolution. CONCLUSION/SIGNIFICANCE: Thus, rapid RT-PCR/ESI-MS analysis can be used to simultaneously identify all species of influenza viruses with clade-level resolution, identify mixed viral populations and monitor global spread and emergence of novel viral genotypes. This high-throughput method promises to become an integral component of influenza surveillance.

  14. Statistical analysis of proteomics, metabolomics, and lipidomics data using mass spectrometry

    CERN Document Server

    Mertens, Bart

    2017-01-01

    This book presents an overview of computational and statistical design and analysis of mass spectrometry-based proteomics, metabolomics, and lipidomics data. This contributed volume provides an introduction to the special aspects of statistical design and analysis with mass spectrometry data for the new omic sciences. The text discusses common aspects of design and analysis between and across all (or most) forms of mass spectrometry, while also providing special examples of application with the most common forms of mass spectrometry. Also covered are applications of computational mass spectrometry not only in clinical study but also in the interpretation of omics data in plant biology studies. Omics research fields are expected to revolutionize biomolecular research by the ability to simultaneously profile many compounds within either patient blood, urine, tissue, or other biological samples. Mass spectrometry is one of the key analytical techniques used in these new omic sciences. Liquid chromatography mass ...

  15. Statistical design of quantitative mass spectrometry-based proteomic experiments.

    Science.gov (United States)

    Oberg, Ann L; Vitek, Olga

    2009-05-01

    We review the fundamental principles of statistical experimental design, and their application to quantitative mass spectrometry-based proteomics. We focus on class comparison using Analysis of Variance (ANOVA), and discuss how randomization, replication and blocking help avoid systematic biases due to the experimental procedure, and help optimize our ability to detect true quantitative changes between groups. We also discuss the issues of pooling multiple biological specimens for a single mass analysis, and calculation of the number of replicates in a future study. When applicable, we emphasize the parallels between designing quantitative proteomic experiments and experiments with gene expression microarrays, and give examples from that area of research. We illustrate the discussion using theoretical considerations, and using real-data examples of profiling of disease.

  16. Mass Spectrometry of Polymer Electrolyte Membrane Fuel Cells

    Science.gov (United States)

    Ostroverkh, Anna; Fiala, Roman; Rednyk, Andrii; Matolín, Vladimír

    2016-01-01

    The chemical analysis of processes inside fuel cells under operating conditions in either direct or inverted (electrolysis) mode and their correlation with potentiostatic measurements is a crucial part of understanding fuel cell electrochemistry. We present a relatively simple yet powerful experimental setup for online monitoring of the fuel cell exhaust (of either cathode or anode side) downstream by mass spectrometry. The influence of a variety of parameters (composition of the catalyst, fuel type or its concentration, cell temperature, level of humidification, mass flow rate, power load, cell potential, etc.) on the fuel cell operation can be easily investigated separately or in a combined fashion. We demonstrate the application of this technique on a few examples of low-temperature (70°C herein) polymer electrolyte membrane fuel cells (both alcohol- and hydrogen-fed) subjected to a wide range of conditions. PMID:28042492

  17. Mass Spectrometry of Polymer Electrolyte Membrane Fuel Cells

    Directory of Open Access Journals (Sweden)

    Viktor Johánek

    2016-01-01

    Full Text Available The chemical analysis of processes inside fuel cells under operating conditions in either direct or inverted (electrolysis mode and their correlation with potentiostatic measurements is a crucial part of understanding fuel cell electrochemistry. We present a relatively simple yet powerful experimental setup for online monitoring of the fuel cell exhaust (of either cathode or anode side downstream by mass spectrometry. The influence of a variety of parameters (composition of the catalyst, fuel type or its concentration, cell temperature, level of humidification, mass flow rate, power load, cell potential, etc. on the fuel cell operation can be easily investigated separately or in a combined fashion. We demonstrate the application of this technique on a few examples of low-temperature (70°C herein polymer electrolyte membrane fuel cells (both alcohol- and hydrogen-fed subjected to a wide range of conditions.

  18. Mass Spectrometry of Polymer Electrolyte Membrane Fuel Cells.

    Science.gov (United States)

    Johánek, Viktor; Ostroverkh, Anna; Fiala, Roman; Rednyk, Andrii; Matolín, Vladimír

    2016-01-01

    The chemical analysis of processes inside fuel cells under operating conditions in either direct or inverted (electrolysis) mode and their correlation with potentiostatic measurements is a crucial part of understanding fuel cell electrochemistry. We present a relatively simple yet powerful experimental setup for online monitoring of the fuel cell exhaust (of either cathode or anode side) downstream by mass spectrometry. The influence of a variety of parameters (composition of the catalyst, fuel type or its concentration, cell temperature, level of humidification, mass flow rate, power load, cell potential, etc.) on the fuel cell operation can be easily investigated separately or in a combined fashion. We demonstrate the application of this technique on a few examples of low-temperature (70°C herein) polymer electrolyte membrane fuel cells (both alcohol- and hydrogen-fed) subjected to a wide range of conditions.

  19. Sequencing of Oligourea Foldamers by Tandem Mass Spectrometry

    Science.gov (United States)

    Bathany, Katell; Owens, Neil W.; Guichard, Gilles; Schmitter, Jean-Marie

    2013-03-01

    This study is focused on sequence analysis of peptidomimetic helical oligoureas by means of tandem mass spectrometry, to build a basis for de novo sequencing for future high-throughput combinatorial library screening of oligourea foldamers. After the evaluation of MS/MS spectra obtained for model compounds with either MALDI or ESI sources, we found that the MALDI-TOF-TOF instrument gave more satisfactory results. MS/MS spectra of oligoureas generated by decay of singly charged precursor ions show major ion series corresponding to fragmentation across both CO-NH and N'H-CO urea bonds. Oligourea backbones fragment to produce a pattern of a, x, b, and y type fragment ions. De novo decoding of spectral information is facilitated by the occurrence of low mass reporter ions, representative of constitutive monomers, in an analogous manner to the use of immonium ions for peptide sequencing.

  20. Differential Rapid Screening of Phytochemicals by Leaf Spray Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, Thomas; Graham Cooks, R. [Univ. of Innsbruck, Innsbruck (Austria)

    2014-03-15

    Ambient ionization can be achieved by generating an electrospray directly from plant tissue ('leaf spray'). The resulting mass spectra are characteristic of ionizable phytochemicals in the plant material. By subtracting the leaf spray spectra recorded from the petals of two hibiscus species H. moscheutos and H. syriacus one gains rapid access to the metabolites that differ most in the two petals. One such compound was identified as the sambubioside of quercitin (or delphinidin) while others are known flavones. Major interest centered on a C{sub 19}H{sub 29}NO{sub 5} compound that occurs only in the large H. moscheutos bloom. Attempts were made to characterize this compound by mass spectrometry alone as a test of such an approach. This showed that the compound is an alkaloid, assigned to the polyhydroxylated pyrrolidine class, and bound via a C{sub 3} hydrocarbon unit to a monoterpene.

  1. Analysis of protein composition using multidimensional chromatography and mass spectrometry.

    Science.gov (United States)

    Link, Andrew J; Washburn, Michael P

    2014-11-03

    Multidimensional liquid chromatography of peptides produced by protease digestion of complex protein mixtures followed by tandem mass spectrometry can be coupled with automated database searching to identify large numbers of proteins in complex samples. These methods avoid the limitations of gel electrophoresis and in-gel digestions by directly identifying protein mixtures in solution. One method used extensively is named Multidimensional Protein Identification Technology (MudPIT), where reversed-phase chromatography and strong cation-exchange chromatography are coupled directly in a microcapillary column. This column is then placed in line between an HPLC and a mass spectrometer for complex mixture analysis. MudPIT remains a powerful approach for analyzing complex mixtures like whole proteomes and protein complexes. MudPIT is used for quantitative proteomic analysis of complex mixtures to generate novel biological insights.

  2. Mass spectrometry. [in organic ion and biorganic chemistry and medicine

    Science.gov (United States)

    Burlingame, A. L.; Cox, R. E.; Derrick, P. J.

    1974-01-01

    Review of the present status of mass spectrometry in the light of pertinent recent publications spanning the period from December 1971 to January 1974. Following an initial survey of techniques, instruments, and computer applications, a sharp distinction is made between the chemistry of organic (radical-)ions and analytical applications in biorganic chemistry and medicine. The emphasis is on the chemistry of organic (radical-)ions at the expense of inorganic, organometallic, and surface ion chemistry. Biochemistry and medicine are chosen because of their contemporary importance and because of the stupendous contributions of mass spectroscopy to these fields in the past two years. In the review of gas-phase organic ion chemistry, special attention is given to studies making significant contributions to the understanding of ion chemistry.

  3. Charge detection mass spectrometry: Instrumentation & applications to viruses

    Science.gov (United States)

    Pierson, Elizabeth E.

    For over three decades, electrospray ionization (ESI) has been used to ionize non-covalent complexes and subsequently transfer the intact ion into the gas phase for mass spectrometry (MS) analysis. ESI generates a distribution of multiple charged ions, resulting in an m/z spectrum comprised of a series of peaks, known as a charge state envelope. To obtain mass information, the number of charges for each peak must be deduced. For smaller biological analytes like peptides, the charge states are sufficiently resolved and this process is straightforward. For macromolecular complexes exceeding ~100 kDa, this process is complicated by the broadening and shifting of charge states due to incomplete desolvation, salt adduction, and inherent mass heterogeneity. As the analyte mass approaches the MDa regime, the m/z spectrum is often comprised of a broad distribution of unresolved charge states. In such cases, mass determination is precluded. Charge detection mass spectrometry (CDMS) is an emerging MS technique for determining the masses of heterogeneous, macromolecular complexes. In CDMS, the m/z and z of single ions are measured concurrently so that mass is easily calculated. With this approach, deconvolution of an m/z spectrum is unnecessary. This measurement is carried out by passing macroions through a conductive cylinder. The induced image charge on the cylindrical detector provides information about m/z and z: the m/z is related to its time-of-flight through the detector, and the z is related to the intensity of the image charge. We have applied CDMS to study the self-assembly of virus capsids. Late-stage intermediates in the assembly of hepatitis B virus, a devastating human pathogen, have been identified. This is the first time that such intermediates have been detected and represent a significant advancement towards understanding virus capsid assembly. CDMS has also been used to identify oversized, non-icosahedral polymorphs in the assembly of woodchuck hepatitis

  4. An ion-to-photon conversion detector for mass spectrometry

    Science.gov (United States)

    Dubois, F.; Knochenmuss, R.; Zenobi, R.

    1997-12-01

    An ion-to-photon conversion detector (IPD) for time-of-flight mass spectrometry was studied and tested with ions produced by matrix-assisted laser desorption-ionization. The detector consisted of a conversion surface located at the end of the drift tube of a time-of-flight mass spectrometer and, behind it, a head-on photomultiplier tube. Fluorescent organic scintillator materials like Bu-PBD [2-(4-t-buthylphenyl)-5-(4-biphenylyl)-1,3,4-oxidiazole] were found to be the most efficient converters of those materials tested. Similar mass resolutions were found with the ion-to-photo detector and standard microchannel plates in a linear time-of-flight instrument. The background noise of the IPD was more intense than with microchannel plates. Slow unfocused ions are suspected to contribute to this noise. Test analytes as large as 70 000 Da could be measured with the IPD. Even with no secondary particle conversion surface in front of the IPD, masses up to approximately 20 000 Da may be more efficiently detected with the IPD than the MCP. For higher masses, a conversion dynode should be considered for increased signal.

  5. High Resolution Mass Spectrometry of Polyfluorinated Polyether-Based Formulation

    Science.gov (United States)

    Dimzon, Ian Ken; Trier, Xenia; Frömel, Tobias; Helmus, Rick; Knepper, Thomas P.; de Voogt, Pim

    2016-02-01

    High resolution mass spectrometry (HRMS) was successfully applied to elucidate the structure of a polyfluorinated polyether (PFPE)-based formulation. The mass spectrum generated from direct injection into the MS was examined by identifying the different repeating units manually and with the aid of an instrument data processor. Highly accurate mass spectral data enabled the calculation of higher-order mass defects. The different plots of MW and the nth-order mass defects (up to n = 3) could aid in assessing the structure of the different repeating units and estimating their absolute and relative number per molecule. The three major repeating units were -C2H4O-, -C2F4O-, and -CF2O-. Tandem MS was used to identify the end groups that appeared to be phosphates, as well as the possible distribution of the repeating units. Reversed-phase HPLC separated of the polymer molecules on the basis of number of nonpolar repeating units. The elucidated structure resembles the structure in the published manufacturer technical data. This analytical approach to the characterization of a PFPE-based formulation can serve as a guide in analyzing not just other PFPE-based formulations but also other fluorinated and non-fluorinated polymers. The information from MS is essential in studying the physico-chemical properties of PFPEs and can help in assessing the risks they pose to the environment and to human health.

  6. Determination of mercury in hair: Comparison between gold amalgamation-atomic absorption spectrometry and mass spectrometry.

    Science.gov (United States)

    Domanico, Francesco; Forte, Giovanni; Majorani, Costanza; Senofonte, Oreste; Petrucci, Francesco; Pezzi, Vincenzo; Alimonti, Alessandro

    2016-09-29

    Mercury is a heavy metal that causes serious health problems in exposed subjects. The most toxic form, i.e., methylmercury (MeHg), is mostly excreted through human hair. Numerous analytical methods are available for total Hg analysis in human hair, including cold vapour atomic fluorescence spectrometry (CV-AFS), inductively coupled plasma mass spectrometry (ICP-MS) and thermal decomposition amalgamation atomic absorption spectrometry (TDA-AAS). The aim of the study was to compare the TDA-AAS with the ICP-MS in the Hg quantification in human hair. After the washing procedure to minimize the external contamination, from each hair sample two aliquots were taken; the first was used for direct analysis of Hg by TDA-AAS and the second was digested for Hg determination by the ICP-MS. Results indicated that the two data sets were fully comparable (median; TDA-AAS, 475ngg(-1); ICP-MS, 437ngg(-1)) and were not statistically different (Mann-Whitney test; p=0.44). The two techniques presented results with a good coefficient of correlation (r=0.94) despite different operative ranges and method limits. Both techniques satisfied internal performance requirements and the parameters for method validation resulting sensitive, precise and reliable. Finally, the use of the TDA-AAS can be considered instead of the ICP-MS in hair analysis in order to reduce sample manipulation with minor risk of contamination, less time consuming due to the absence of the digestion step and cheaper analyses.

  7. Coherent pipeline for biomarker discovery using mass spectrometry and bioinformatics

    Directory of Open Access Journals (Sweden)

    Al-Shahib Ali

    2010-08-01

    Full Text Available Abstract Background Robust biomarkers are needed to improve microbial identification and diagnostics. Proteomics methods based on mass spectrometry can be used for the discovery of novel biomarkers through their high sensitivity and specificity. However, there has been a lack of a coherent pipeline connecting biomarker discovery with established approaches for evaluation and validation. We propose such a pipeline that uses in silico methods for refined biomarker discovery and confirmation. Results The pipeline has four main stages: Sample preparation, mass spectrometry analysis, database searching and biomarker validation. Using the pathogen Clostridium botulinum as a model, we show that the robustness of candidate biomarkers increases with each stage of the pipeline. This is enhanced by the concordance shown between various database search algorithms for peptide identification. Further validation was done by focusing on the peptides that are unique to C. botulinum strains and absent in phylogenetically related Clostridium species. From a list of 143 peptides, 8 candidate biomarkers were reliably identified as conserved across C. botulinum strains. To avoid discarding other unique peptides, a confidence scale has been implemented in the pipeline giving priority to unique peptides that are identified by a union of algorithms. Conclusions This study demonstrates that implementing a coherent pipeline which includes intensive bioinformatics validation steps is vital for discovery of robust biomarkers. It also emphasises the importance of proteomics based methods in biomarker discovery.

  8. Secondary ionization mass spectrometry analysis in petrochronology: Chapter 7

    Science.gov (United States)

    Schmitt, Axel K.; Vazquez, Jorge A.

    2017-01-01

    The goal of petrochronology is to extract information about the rates and conditions at which rocks and magmas are transported through the Earth’s crust. Garnering this information from the rock record greatly benefits from integrating textural and compositional data with radiometric dating of accessory minerals. Length scales of crystal growth and diffusive transport in accessory minerals under realistic geologic conditions are typically in the range of 1–10’s of μm, and in some cases even substantially smaller, with zircon having among the lowest diffusion coefficients at a given temperature (e.g., Cherniak and Watson 2003). Intrinsic to the compartmentalization of geochemical and geochronologic information from intra-crystal domains is the requirement to determine accessory mineral compositions using techniques that sample at commensurate spatial scales so as to not convolute the geologic signals that are recorded within crystals, as may be the case with single grain or large grain fragment analysis by isotope dilution thermal ionization mass spectrometry (ID-TIMS; e.g., Schaltegger and Davies 2017, this volume; Schoene and Baxter 2017, this volume). Small crystals can also be difficult to extract by mineral separation techniques traditionally used in geochronology, which also lead to a loss of petrographic context. Secondary Ionization Mass Spectrometry, that is SIMS performed with an ion microprobe, is an analytical technique ideally suited to meet the high spatial resolution analysis requirements that are critical for petrochronology (Table 1).

  9. Isotope determination of sulfur by mass spectrometry in soil samples

    Directory of Open Access Journals (Sweden)

    Alexssandra Luiza Rodrigues Molina Rossete

    2012-12-01

    Full Text Available Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-, which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2- concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms was carried out by isotope ratio mass spectrometry (IRMS. In this work, the labeled material (K2(34SO4 was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.

  10. Bio-Aerosol Detection Using Mass Spectrometry: Public Health Applications

    Energy Technology Data Exchange (ETDEWEB)

    Ludvigson, Laura D. [Univ. of California, Berkeley, CA (United States)

    2004-01-01

    I recently spent a summer as an intern at the Lawrence Livermore National Laboratory. I worked on a project involving the real-time, reagentless, single cell detection of aerosolized pathogens using a novel mass spectrometry approach called Bio-Aerosol Mass Spectrometry (BAMS). Based upon preliminary results showing the differentiation capabilities of BAMS, I would like to explore the development and use of this novel detection system in the context of both environmental and clinical sample pathogen detection. I would also like to explore the broader public health applications that a system such as BAMS might have in terms of infectious disease prevention and control. In order to appreciate the potential of this instrument, I will demonstrate the need for better pathogen detection methods, and outline the instrumentation, data analysis and preliminary results that lead me toward a desire to explore this technology further. I will also discuss potential experiments for the future along with possible problems that may be encountered along the way.

  11. Analysis of hazardous biological material by MALDI mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    KL Wahl; KH Jarman; NB Valentine; MT Kingsley; CE Petersen; ST Cebula; AJ Saenz

    2000-03-21

    Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-MS) has become a valuable tool for analyzing microorganisms. The speed with which data can be obtained from MALDI-MS makes this a potentially important tool for biological health hazard monitoring and forensic applications. The excitement in the mass spectrometry community in this potential field of application is evident by the expanding list of research laboratories pursuing development of MALDI-MS for bacterial identification. Numerous research groups have demonstrated the ability to obtain unique MALDI-MS spectra from intact bacterial cells and bacterial cell extracts. The ability to differentiate strains of the same species has been investigated. Reproducibility of MALDI-MS spectra from bacterial species under carefully controlled experimental conditions has also been demonstrated. Wang et al. have reported on interlaboratory reproducibility of the MALDI-MS analysis of several bacterial species. However, there are still issues that need to be addressed, including the careful control of experimental parameters for reproducible spectra and selection of optimal experimental parameters such as solvent and matrix.

  12. NMR and mass spectrometry of phosphorus in wetlands

    Science.gov (United States)

    El-Rifai, H.; Heerboth, M.; Gedris, T.E.; Newman, S.; Orem, W.; Cooper, W.T.

    2008-01-01

    There is at present little information on the long-term stability of phosphorus sequestered in wetlands. Phosphorus sequestered during high loading periods may be relatively unstable and easily remobilized following changes in nutrient status or hydrological regime, but the chemical forms of sequestered phosphorus that do remobilize are largely unknown at this time. A lack of suitable analytical techniques has contributed to this dearth of knowledge regarding the stability of soil organic phosphorus. We analysed phosphorus in soils from the 'head' of Rescue Strand tree island and an adjacent marsh in the Florida Everglades by 31P nuclear magnetic resonance (NMR) spectroscopy and high-resolution mass spectrometry. Tree islands are important areas of biodiversity within the Everglades and offer a unique opportunity to study phosphorus sequestration because they are exposed to large phosphorus loads and appear to be natural nutrient sinks. The 31P NMR profiling of extracts from surface and sediment samples in the tree island indicates that phosphorus input to Rescue Strand tree island soils is mostly in the form of inorganic ortho-phosphate and is either refractory when deposited or rapidly recycled by the native vegetation into a stable phosphorus pool largely resistant to re-utilization by plants or microbes. Mass spectrometry revealed the presence of inositol hexakisphosphate, a common organic monophosphate ester not previously observed in Everglades' soils. ?? 2008 The Authors.

  13. Expanded newborn screening by mass spectrometry: New tests, future perspectives.

    Science.gov (United States)

    Ombrone, Daniela; Giocaliere, Elisa; Forni, Giulia; Malvagia, Sabrina; la Marca, Giancarlo

    2016-01-01

    Tandem mass spectrometry (MS/MS) has become a leading technology used in clinical chemistry and has shown to be particularly sensitive and specific when used in newborn screening (NBS) tests. The success of tandem mass spectrometry is due to important advances in hardware, software and clinical applications during the last 25 years. MS/MS permits a very rapid measurement of many metabolites in different biological specimens by using filter paper spots or directly on biological fluids. Its use in NBS give us the chance to identify possible treatable metabolic disorders even when asymptomatic and the benefits gained by this type of screening is now recognized worldwide. Today the use of MS/MS for second-tier tests and confirmatory testing is promising especially in the early detection of new disorders such as some lysosomal storage disorders, ADA and PNP SCIDs, X-adrenoleucodistrophy (X-ALD), Wilson disease, guanidinoacetate methyltransferase deficiency (GAMT), and Duchenne muscular dystrophy. The new challenge for the future will be reducing the false positive rate by using second-tier tests, avoiding false negative results by using new specific biomarkers and introducing new treatable disorders in NBS programs.

  14. Optimal selection of epitopes for TXP-immunoaffinity mass spectrometry

    Directory of Open Access Journals (Sweden)

    Joos Thomas

    2010-06-01

    Full Text Available Abstract Background Mass spectrometry (MS based protein profiling has become one of the key technologies in biomedical research and biomarker discovery. One bottleneck in MS-based protein analysis is sample preparation and an efficient fractionation step to reduce the complexity of the biological samples, which are too complex to be analyzed directly with MS. Sample preparation strategies that reduce the complexity of tryptic digests by using immunoaffinity based methods have shown to lead to a substantial increase in throughput and sensitivity in the proteomic mass spectrometry approach. The limitation of using such immunoaffinity-based approaches is the availability of the appropriate peptide specific capture antibodies. Recent developments in these approaches, where subsets of peptides with short identical terminal sequences can be enriched using antibodies directed against short terminal epitopes, promise a significant gain in efficiency. Results We show that the minimal set of terminal epitopes for the coverage of a target protein list can be found by the formulation as a set cover problem, preceded by a filtering pipeline for the exclusion of peptides and target epitopes with undesirable properties. Conclusions For small datasets (a few hundred proteins it is possible to solve the problem to optimality with moderate computational effort using commercial or free solvers. Larger datasets, like full proteomes require the use of heuristics.

  15. Bio-Aerosol Detection Using Mass Spectrometry: Public Health Applications

    Energy Technology Data Exchange (ETDEWEB)

    Ludvigson, L D

    2004-03-05

    I recently spent a summer as an intern at the Lawrence Livermore National Laboratory. I worked on a project involving the real-time, reagentless, single cell detection of aerosolized pathogens using a novel mass spectrometry approach called Bio-Aerosol Mass Spectrometry (BAMS). Based upon preliminary results showing the differentiation capabilities of BAMS, I would like to explore the development and use of this novel detection system in the context of both environmental and clinical sample pathogen detection. I would also like to explore the broader public health applications that a system such as BAMS might have in terms of infectious disease prevention and control. In order to appreciate the potential of this instrument, I will demonstrate the need for better pathogen detection methods, and outline the instrumentation, data analysis and preliminary results that lead me toward a desire to explore this technology further. I will also discuss potential experiments for the future along with possible problems that may be encountered along the way.

  16. Rapid Detection of Irreversible Acetylcholineasterase Inhibitor by Mass Spectrometry Assay

    Institute of Scientific and Technical Information of China (English)

    蔡婷婷; 张立; 汪蓉; 梁晨; 赵武生; 傅得锋; 张玉荣; 郭寅龙

    2012-01-01

    Here we developed a rapid method to detect acetylcholinesterase (ACHE) activity by matrix-assisted laser de- sorption/ionization Fourier transform mass spectrometry (MALDI-FTMS) for screening irreversible AChE inhibi- tors. Due to its good salt-tolerance and low sample consumption, MALDI-FTMS could facilitate rapid detection, especially detection in real application. AChE activity was determined through calculating abundance of substrate and product in mass spectrometry. By this approach, we investigated the relation of organophosphorous (OP) con- centrations and AChE inhibition. Shown in different inhibition curves from different OP pesticides, enzyme inhibi- tions still kept good correlation with concentration of OPs. Finally, this AChE-inhibited method was applied to screen whole bloods of four decedents and discuss their death reason. In contrast to healthy persons, three of dece- dents showed low AChE activity, and probably died for irreversible AChE inhibitors. Through the following de- tecting in GC-MS/MS, the possible death reason of these three decedents was confirmed, and another decedent actually died for sumicidin, a non-AChE inhibitor. It demonstrated that screening irreversible AChE inhibitors by detecting enzyme activity in MALDI-FTMS provided fast and accurate analysis results and excluded another toxicants not functioning on ACHE. This method offered alternative choices for indicating the existence of enzyme inhibitors.

  17. Quantitating subcellular metabolism with multi-isotope imaging mass spectrometry

    Science.gov (United States)

    Steinhauser, Matthew L.; Bailey, Andrew; Senyo, Samuel E.; Guillermier, Christelle; Perlstein, Todd S.; Gould, Alex P.; Lee, Richard T.; Lechene, Claude P.

    2011-01-01

    Mass spectrometry with stable isotope labels has been seminal in discovering the dynamic state of living matter1,2 but is limited to bulk tissues or cells. We developed multi-isotope imaging mass spectrometry (MIMS) that allowed us to view and measure stable isotope incorporation with sub-micron resolution3,4. Here we apply MIMS to diverse organisms, including Drosophila, mice, and humans. We test the “immortal strand hypothesis,” which predicts that during asymmetric stem cell division chromosomes containing older template DNA are segregated to the daughter destined to remain a stem cell, thus insuring lifetime genetic stability. After labeling mice with 15N-thymidine from gestation through post-natal week 8, we find no 15N label retention by dividing small intestinal crypt cells after 4wk chase. In adult mice administered 15N-thymidine pulse-chase, we find that proliferating crypt cells dilute label consistent with random strand segregation. We demonstrate the broad utility of MIMS with proof-of-principle studies of lipid turnover in Drosophila and translation to the human hematopoietic system. These studies show that MIMS provides high-resolution quantitation of stable isotope labels that cannot be obtained using other techniques and that is broadly applicable to biological and medical research. PMID:22246326

  18. Proteolysis in microfluidic droplets: an approach to interface protein separation and peptide mass spectrometry.

    Science.gov (United States)

    Ji, Ji; Nie, Lei; Qiao, Liang; Li, Yixin; Guo, Liping; Liu, Baohong; Yang, Pengyuan; Girault, Hubert H

    2012-08-07

    A versatile microreactor protocol based on microfluidic droplets has been developed for on-line protein digestion. Proteins separated by liquid chromatography are fractionated in water-in-oil droplets and digested in sequence. The microfluidic reactor acts also as an electrospray ionization emitter for mass spectrometry analysis of the peptides produced in the individual droplets. Each droplet is an enzymatic micro-reaction unit with efficient proteolysis due to rapid mixing, enhanced mass transfer and automated handling. This droplet approach eliminates sample loss, cross-contamination, non-specific absorption and memory effect. A protein mixture was successfully identified using the droplet-based micro-reactor as interface between reverse phase liquid chromatography and mass spectrometry.

  19. Application of mass spectrometry-based proteomics techniques for the detection of protein doping in sports.

    Science.gov (United States)

    Kay, Richard G; Creaser, Colin S

    2010-04-01

    Mass spectrometry-based proteomic approaches have been used to develop methodologies capable of detecting the abuse of protein therapeutics such as recombinant human erythropoietin and recombinant human growth hormone. Existing detection methods use antibody-based approaches that, although effective, suffer from long assay development times and specificity issues. The application of liquid chromatography with tandem mass spectrometry and selected reaction-monitoring-based analysis has demonstrated the ability to detect and quantify existing protein therapeutics in plasma. Furthermore, the multiplexing capability of selected reaction-monitoring analysis has also aided in the detection of multiple downstream biomarkers in a single analysis, requiring less sample than existing immunological techniques. The flexibility of mass spectrometric instrumentation has shown that the technique is capable of detecting the abuse of novel and existing protein therapeutics, and has a vital role in the fight to keep sports drug-free.

  20. Plutonium Isotopes ((239-241)Pu) Dissolved in Pacific Ocean Waters Detected by Accelerator Mass Spectrometry: No Effects of the Fukushima Accident Observed.

    Science.gov (United States)

    Hain, Karin; Faestermann, Thomas; Fimiani, Leticia; Golser, Robin; Gómez-Guzmán, José Manuel; Korschinek, Gunther; Kortmann, Florian; Lierse von Gostomski, Christoph; Ludwig, Peter; Steier, Peter; Tazoe, Hirofumi; Yamada, Masatoshi

    2017-02-21

    The concentration of plutonium (Pu) and the isotopic ratios of (240)Pu to (239)Pu and (241)Pu to (239)Pu were determined by accelerator mass spectrometry (AMS) in Pacific Ocean water samples (20 L each) collected in late 2012. The isotopic Pu ratios are important indicators of different contamination sources and were used to identify a possible release of Pu into the ocean by the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident. In particular, (241)Pu is a well-suited indicator for a recent entry of Pu because (241)Pu from fallout of nuclear weapon testings has already significantly decayed. A total of 10 ocean water samples were prepared at the Radiochemie München of the TUM and analyzed at the Vienna Environmental Research Laboratory (VERA). Several samples showed a slightly elevated (240)Pu/(239)Pu ratio of up to 0.22 ± 0.02 compared to global fallout ((240)Pu/(239)Pu = 0.180 ± 0.007), whereas all measured (241)Pu-to-(239)Pu ratios were consistent with nuclear weapon fallout ((241)Pu/(239)Pu < 2.4 × 10(-3)), which means that no impact from the Fukushima accident was detected. From the average (241)Pu-to-(239)Pu ratio of 8-2(+3) ×10(-4) at a sampling station located at a distance of 39.6 km to FDNPP, the 1-σ upper limit for the FDNPP contribution to the (239)Pu inventory in the water column was estimated to be 0.2%. Pu, with the signature of weapon-grade Pu was found in a single sample collected around 770 km off the west coast of the United States.

  1. Effect of the methyl substitution on the combustion of two methylheptane isomers: Flame chemistry using vacuum-ultraviolet (VUV) photoionization mass spectrometry

    KAUST Repository

    Selim, Hatem

    2015-04-16

    Alkanes with one or more methyl substitutions are commonly found in liquid transportation fuels, so a fundamental investigation of their combustion chemistry is warranted. In the present work, stoichiometric low-pressure (20 Torr) burner-stabilized flat flames of 2-methylheptane and 3-methylheptane were investigated. Flame species were measured via time-of-flight molecular-beam mass spectrometry, with vacuum-ultraviolet (VUV) synchrotron radiation as the ionization source. Mole fractions of major end-products and intermediate species (e.g., alkanes, alkenes, alkynes, aldehydes, and dienes) were quantified axially above the burner surface. Mole fractions of several free radicals were also measured (e.g., CH3, HCO, C2H3, C3H3, and C3H5). Isomers of different species were identified within the reaction pool by an energy scan between 8 and 12 eV at a distance of 2.5 mm away from the burner surface. The role of methyl substitution location on the alkane chain was determined via comparisons of similar species trends obtained from both flames. The results revealed that the change in CH3 position imposed major differences on the combustion of both fuels. Comparison with numerical simulations was performed for kinetic model testing. The results provide a comprehensive set of data about the combustion of both flames, which can enhance the erudition of both fuels combustion chemistry and also improve their chemical kinetic reaction mechanisms. © 2015 American Chemical Society.

  2. Determination of o,oEDDHA - a xenobiotic chelating agent used in Fe fertilizers - in plant tissues by liquid chromatography/electrospray mass spectrometry: overcoming matrix effects.

    Science.gov (United States)

    Orera, Irene; Abadía, Anunciación; Abadía, Javier; Alvarez-Fernández, Ana

    2009-06-01

    The Fe(III)-chelate of ethylenediamine-N,N'-bis(o-hydroxyphenylacetic) acid (o,oEDDHA) is generally considered as the most efficient and widespread Fe fertilizer for fruit crops and intensive horticulture. The determination of the xenobiotic chelating agent o,oEDDHA inside the plant is a key issue in the study of this fertilizer. Both the low concentrations of o,oEDDHA expected and the complexity of plant matrices have been important drawbacks in the development of analytical methods for the determination of o,oEDDHA in plant tissues. The determination of o,oEDDHA in plant materials has been tackled in this study by liquid chromatography coupled to mass spectrometry using several plant species and tissues. Two types of internal standards have been tested: Iron stable isotope labeled compounds and a structural analogue compound, the Fe(III) chelate of ethylenediamine-N,N'-bis(2-hydroxy-4-methylphenylacetic) acid (o,oEDDHMA). Iron stable isotope labeled internal standards did not appear to be suitable because of the occurrence of isobaric endogenous compounds and/or isotope exchange reactions between plant native Fe pools and the Fe stable isotope of the internal standard. However, the structural analogue Fe(III)-o,oEDDHMA is an adequate internal standard for the determination of both isomers of o,oEDDHA (racemic and meso) in plant tissues. The method was highly sensitive, with limits of detection and quantification in the range of 3-49 and 11-162 pmol g(-1) fresh weight, respectively, and analyte recoveries were in the range of 74-116%. Using this methodology, both o,oEDDHA isomers were found in all tissues of sugar beet and tomato plants treated with 90 microM Fe(III)-o,oEDDHA for 24 h, including leaves, roots and xylem sap. This methodology constitutes a useful tool for studies on o,oEDDHA plant uptake, transport and allocation.

  3. Effects of packaging materials on the aroma stability of Thai 'tom yam' seasoning powder as determined by descriptive sensory analysis and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Leelaphiwat, Pattarin; Harte, Janice B; Auras, Rafael A; Ong, Peter Kc; Chonhenchob, Vanee

    2017-04-01

    Changes in the aroma characteristics of Thai 'tom yam' seasoning powder, containing lemongrass, galangal and kaffir lime leaf, as affected by different packaging materials were assessed using quantitative descriptive analysis (QDA) and gas chromatography-mass spectrometry (GC-MS). The descriptive aroma attributes for lemongrass, galangal and kaffir lime leaf powders were developed by the QDA panel. The mixed herb and spice seasoning powder was kept in glass jars closed with different packaging materials (Nylon 6, polyethylene terephthalate (PET) and polylactic acid (PLA)) stored at 38 °C (accelerated storage condition), and evaluated by the trained QDA panel during storage for 49 days. The descriptive words for Thai 'tom yam' seasoning powder developed by the trained panelists were lemongrass, vinegary and leafy for lemongrass, galangal and kaffir lime leaf dried powder, respectively. The aroma intensities significantly (P ≤ 0.05) decreased with increased storage time. However, the intensity scores for aroma attributes were not significantly (P > 0.05) different among the packaging materials studied. The major components in Thai 'tom yam' seasoning powder, quantified by GC-MS, were estragole, bicyclo[3.1.1]heptane, β-bisabolene, benzoic acid and 2-ethylhexyl salicylate. The concentrations of major aroma compounds significantly (P ≤ 0.05) decreased with storage time. Aroma stability of Thai 'tom yam' powder can be determined by descriptive sensory evaluation and GC-MS analysis. Nylon, PET and PLA exhibited similar aroma barrier properties against key aroma compounds in Thai 'tom yam'. This information can be used for prediction of aroma loss through packaging materials during storage of Thai 'tom yam'. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  4. Elucidation of the mass fragmentation pathways of potato glycoalkaloids and aglycons using Orbitrap mass spectrometry.

    Science.gov (United States)

    Cahill, Michael G; Caprioli, Giovanni; Vittori, Sauro; James, Kevin J

    2010-09-01

    The mass fragmentation of potato glycoalkaloids, α-solanine and α-chaconine, and the aglycons, demissidine and solasodine were studied using the Orbitrap Fourier transform (FT) mass spectrometer. Using the linear ion trap (LIT) mass spectrometry, multistage collisional-induced dissociation (CID) experiments (MS(n)) on the [M + H](+) precursor ions were performed to aid the elucidation of the mass fragmentation pathways. In addition, higher energy collisional-induced dissociation (HCD) mass spectra were generated for these toxins at a high resolution setting [100,000 FWHM (full width at half maximum)] using the Orbitrap. This hybrid mass spectrometry instrumentation was exploited to produce MS(3) spectra by selecting MS(2) product ions, generated using LIT MS, and fragmentation using HCD. The accurate mass data in the MS(3) spectra aided the confirmation of proposed product ion formulae. The precursor and product ions from glycoalkaloids lost up to four sugars from different regions during MS(n) experiments. Mass fragmentation of the six-ring aglycons were similar, generating major product ions that resulted from cleavages at the B-rings and E-rings.

  5. Development of High Performance Liquid Chromatography and Mass Spectrometry:a Key Engine of TCM Modernization

    Institute of Scientific and Technical Information of China (English)

    Zheng-Xiang Zhang; Xue Qiao; Min Ye; Man-Yu Zhang; Yue Song; Tao Bo

    2015-01-01

    Traditional Chinese Medicine (TCM) has been popular for thousand years in prevention and treatment of chronic diseases synergistically with Western medicine while producing mild healing effects and lower side effects. Although many TCMs have been proven effective by modern pharmacological studies and clinical trials, their bioactive constituents and the remedial mechanisms are still not well understood. Researchers have made great efforts to explore the real theory of TCM for many years with different strategies. Development of high performance liquid chromatography (HPLC) and mass spectrometry within recent decade can provide scientists with robust technologies for disclosing the mysterious mask of TCM. In this paper, important innovations of HPLC and mass spectrometry are reviewed in the application of TCM analysis from single compound identification to metabolomic strategy.

  6. Multi-residue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry: optimisation and matrix effects reduction by quick, easy, cheap, effective, rugged and safe extraction.

    Science.gov (United States)

    Bourdat-Deschamps, Marjolaine; Leang, Sokha; Bernet, Nathalie; Daudin, Jean-Jacques; Nélieu, Sylvie

    2014-07-04

    The aim of this study was to develop and optimise an analytical method for the quantification of a bactericide and 13 pharmaceutical products, including 8 antibiotics (fluoroquinolones, tetracyclines, sulfonamides, macrolide), in various aqueous environmental samples: soil water and aqueous fractions of pig slurry, digested pig slurry and sewage sludge. The analysis was performed by online solid-phase extraction coupled to ultra-high performance liquid chromatography with tandem mass spectrometry (online SPE-UHPLC-MS-MS). The main challenge was to minimize the matrix effects observed in mass spectrometry, mostly due to ion suppression. They depended on the dissolved organic carbon (DOC) content and its origin, and ranged between -22% and +20% and between -38% and -93% of the signal obtained without matrix, in soil water and slurry supernatant, respectively. The very variable levels of these matrix effects suggested DOC content cut-offs above which sample purification was required. These cut-offs depended on compounds, with concentrations ranging from 30 to 290mgC/L for antibiotics (except tylosine) up to 600-6400mgC/L for the most apolar compounds. A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction procedure was therefore optimised using an experimental design methodology, in order to purify samples with high DOC contents. Its performance led to a compromise, allowing fluoroquinolone and tetracycline analysis. The QuEChERS extraction salts consisted therefore of sodium acetate, sodium sulfate instead of magnesium sulfate, and sodium ethylenediaminetetraacetate (EDTA) as a ligand of divalent cations. The modified QuEChERS procedure employed for the extraction of pharmaceuticals in slurry and digested slurry liquid phases reduced the matrix effects for almost all the compounds, with extraction recoveries generally above 75%. The performance characteristics of the method were evaluated in terms of linearity, intra-day and inter

  7. Ion Mobility Spectrometry - High Resolution LTQ-Orbitrap Mass Spectrometry for Analysis of Homemade Explosives

    Science.gov (United States)

    Hagan, Nathan; Goldberg, Ilana; Graichen, Adam; St. Jean, Amanda; Wu, Ching; Lawrence, David; Demirev, Plamen

    2017-08-01

    The detailed chemical characterization of homemade explosives (HMEs) and other chemicals that can mimic or mask the presence of explosives is important for understanding and improving the performance of commercial instrumentation used for explosive detection. To that end, an atmospheric-pressure drift tube ion mobility spectrometry (IMS) instrument has been successfully coupled to a commercial tandem mass spectrometry (MS) system. The tandem MS system is comprised of a linear ion trap and a high resolution Orbitrap analyzer. This IMS-MS combination allows extensive characterization of threat chemical compounds, including HMEs, and complex real-world background chemicals that can interfere with detection. Here, the composition of ion species originating from a specific HME, erythritol tetranitrate, has been elucidated using accurate mass measurements, isotopic ratios, and tandem MS. Gated IMS-MS and high-resolution MS have been used to identify minor impurities that can be indicative of the HME source and/or synthesis route. Comparison between data obtained on the IMS/MS system and on commercial stand-alone IMS instruments used as explosive trace detectors (ETDs) has also been performed. Such analysis allows better signature assignments of threat compounds, modified detection algorithms, and improved overall ETD performance.

  8. Simultaneous Proteomic Discovery and Targeted Monitoring using Liquid Chromatography, Ion Mobility Spectrometry, and Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Burnum-Johnson, Kristin E.; Nie, Song; Casey, Cameron P.; Monroe, Matthew E.; Orton, Daniel J.; Ibrahim, Yehia M.; Gritsenko, Marina A.; Clauss, Therese R. W.; Shukla, Anil K.; Moore, Ronald J.; Purvine, Samuel O.; Shi, Tujin; Qian, Weijun; Liu, Tao; Baker, Erin S.; Smith, Richard D.

    2016-09-25

    Current proteomics approaches are comprised of both broad discovery measurements as well as more quantitative targeted measurements. These two different measurement types are used to initially identify potentially important proteins (e.g., candidate biomarkers) and then enable improved quantification for a limited number of selected proteins. However, both approaches suffer from limitations, particularly the lower sensitivity, accuracy, and quantitation precision for discovery approaches compared to targeted approaches, and the limited proteome coverage provided by targeted approaches. Herein, we describe a new proteomics approach that allows both discovery and targeted monitoring (DTM) in a single analysis using liquid chromatography, ion mobility spectrometry and mass spectrometry (LC-IMS-MS). In DTM, heavy labeled peptides for target ions are spiked into tryptic digests and both the labeled and unlabeled peptides are broadly detected using LC-IMS-MS instrumentation, allowing the benefits of discovery and targeted approaches. To understand the possible improvement of the DTM approach, it was compared to LC-MS broad measurements using an accurate mass and time tag database and selected reaction monitoring (SRM) targeted measurements. The DTM results yielded greater peptide/protein coverage and a significant improvement in the detection of lower abundance species compared to LC-MS discovery measurements. DTM was also observed to have similar detection limits as SRM for the targeted measurements indicating its potential for combining the discovery and targeted approaches.

  9. Non-Target Screening of Veterinary Drugs Using Tandem Mass Spectrometry on SmartMass

    Science.gov (United States)

    Xia, Bing; Liu, Xin; Gu, Yu-Cheng; Zhang, Zhao-Hui; Wang, Hai-Yan; Ding, Li-Sheng; Zhou, Yan

    2013-05-01

    Non-target screening of veterinary drugs using tandem mass spectrometric data was performed on the SmartMass platform. This newly developed software uses the characteristic fragmentation patterns (CFP) to identify chemicals, especially those containing particular substructures. A mixture of 17 sulfonamides was separated by ultra performance liquid chromatography (UPLC), and SmartMass was used to process the tandem mass spectrometry (MS/MS) data acquired on an Orbitrap mass spectrometer. The data were automatically extracted, and each sulfonamide was recognized and analyzed with a prebuilt analysis rule. By using this software, over 98 % of the false candidate structures were eliminated, and all the correct structures were found within the top 10 of the ranking lists. Furthermore, SmartMass could also be used to identify slightly modified contraband drugs and metabolites with simple prebuilt rules. [Figure not available: see fulltext.

  10. Laser desorption lamp ionization source for ion trap mass spectrometry.

    Science.gov (United States)

    Wu, Qinghao; Zare, Richard N

    2015-01-01

    A two-step laser desorption lamp ionization source coupled to an ion trap mass spectrometer (LDLI-ITMS) has been constructed and characterized. The pulsed infrared (IR) output of an Nd:YAG laser (1064 nm) is directed to a target inside a chamber evacuated to ~15 Pa causing desorption of molecules from the target's surface. The desorbed molecules are ionized by a vacuum ultraviolet (VUV) lamp (filled with xenon, major wavelength at 148 nm). The resulting ions are stored and detected in a three-dimensional quadrupole ion trap modified from a Finnigan Mat LCQ mass spectrometer operated at a pressure of ≥ 0.004 Pa. The limit of detection for desorbed coronene molecules is 1.5 pmol, which is about two orders of magnitude more sensitive than laser desorption laser ionization mass spectrometry using a fluorine excimer laser (157 nm) as the ionization source. The mass spectrum of four standard aromatic compounds (pyrene, coronene, rubrene and 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (OPC)) shows that parent ions dominate. By increasing the infrared laser power, this instrument is capable of detecting inorganic compounds.

  11. Super-atmospheric pressure chemical ionization mass spectrometry.

    Science.gov (United States)

    Chen, Lee Chuin; Rahman, Md Matiur; Hiraoka, Kenzo

    2013-03-01

    Super-atmospheric pressure chemical ionization (APCI) mass spectrometry was performed using a commercial mass spectrometer by pressurizing the ion source with compressed air up to 7 atm. Similar to typical APCI source, reactant ions in the experiment were generated with corona discharge using a needle electrode. Although a higher needle potential was necessary to initiate the corona discharge, discharge current and detected ion signal were stable at all tested pressures. A Roots booster pump with variable pumping speed was installed between the evacuation port of the mass spectrometer and the original rough pumps to maintain a same pressure in the first pumping stage of the mass spectrometer regardless of ion source pressure. Measurement of gaseous methamphetamine and research department explosive showed an increase in ion intensity with the ion source pressure until an optimum pressure at around 4-5 atm. Beyond 5 atm, the ion intensity decreased with further increase of pressure, likely due to greater ion losses inside the ion transport capillary. For benzene, it was found that besides molecular ion and protonated species, ion due to [M + 2H](+) which was not so common in APCI, was also observed with high ion abundance under super-atmospheric pressure condition.

  12. Method for predicting peptide detection in mass spectrometry

    Science.gov (United States)

    Kangas, Lars [West Richland, WA; Smith, Richard D [Richland, WA; Petritis, Konstantinos [Richland, WA

    2010-07-13

    A method of predicting whether a peptide present in a biological sample will be detected by analysis with a mass spectrometer. The method uses at least one mass spectrometer to perform repeated analysis of a sample containing peptides from proteins with known amino acids. The method then generates a data set of peptides identified as contained within the sample by the repeated analysis. The method then calculates the probability that a specific peptide in the data set was detected in the repeated analysis. The method then creates a plurality of vectors, where each vector has a plurality of dimensions, and each dimension represents a property of one or more of the amino acids present in each peptide and adjacent peptides in the data set. Using these vectors, the method then generates an algorithm from the plurality of vectors and the calculated probabilities that specific peptides in the data set were detected in the repeated analysis. The algorithm is thus capable of calculating the probability that a hypothetical peptide represented as a vector will be detected by a mass spectrometry based proteomic platform, given that the peptide is present in a sample introduced into a mass spectrometer.

  13. Direct Analysis in Real Time (DART) of an Organothiophosphate at Ultrahigh Resolution by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Tandem Mass Spectrometry.

    Science.gov (United States)

    Prokai, Laszlo; Stevens, Stanley M

    2016-01-16

    Direct analysis in real time (DART) is a recently developed ambient ionization technique for mass spectrometry to enable rapid and sensitive analyses with little or no sample preparation. After swab-based field sampling, the organothiophosphate malathion was analyzed using DART-Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Mass resolution was documented to be over 800,000 in full-scan MS mode and over 1,000,000 for an MS/MS product ion produced by collision-induced dissociation of the protonated analyte. Mass measurement accuracy below 1 ppm was obtained for all DART-generated ions that belonged to the test compound in the mass spectra acquired using only external mass calibration. This high mass measurement accuracy, achievable at present only through FTMS, was required for unequivocal identification of the corresponding molecular formulae.

  14. Transitioning from Targeted to Comprehensive Mass Spectrometry Using Genetic Algorithms

    Science.gov (United States)

    Jaffe, Jacob D.; Feeney, Caitlin M.; Patel, Jinal; Lu, Xiaodong; Mani, D. R.

    2016-11-01

    Targeted proteomic assays are becoming increasingly popular because of their robust quantitative applications enabled by internal standardization, and they can be routinely executed on high performance mass spectrometry instrumentation. However, these assays are typically limited to 100s of analytes per experiment. Considerable time and effort are often expended in obtaining and preparing samples prior to targeted analyses. It would be highly desirable to detect and quantify 1000s of analytes in such samples using comprehensive mass spectrometry techniques (e.g., SWATH and DIA) while retaining a high degree of quantitative rigor for analytes with matched internal standards. Experimentally, it is facile to port a targeted assay to a comprehensive data acquisition technique. However, data analysis challenges arise from this strategy concerning agreement of results from the targeted and comprehensive approaches. Here, we present the use of genetic algorithms to overcome these challenges in order to configure hybrid targeted/comprehensive MS assays. The genetic algorithms are used to select precursor-to-fragment transitions that maximize the agreement in quantification between the targeted and the comprehensive methods. We find that the algorithm we used provided across-the-board improvement in the quantitative agreement between the targeted assay data and the hybrid comprehensive/targeted assay that we developed, as measured by parameters of linear models fitted to the results. We also found that the algorithm could perform at least as well as an independently-trained mass spectrometrist in accomplishing this task. We hope that this approach will be a useful tool in the development of quantitative approaches for comprehensive proteomics techniques.

  15. Screening Non-colored Phenolics in Red Wines using Liquid Chromatography/Ultraviolet and Mass Spectrometry/Mass Spectrometry Libraries

    Directory of Open Access Journals (Sweden)

    Changqing Duan

    2007-03-01

    Full Text Available Liquid chromatography/ultraviolet (LC/UV and mass spectrometry/mass spectrometry (MS/MS libraries containing 39 phenolic compounds were established by coupling a LC and an ion trap MS with an electrospray ionization (ESI source, operated in negative ion mode. As a result, the deprotonated [M-H]- molecule was observed for all the analyzed compounds. Using MS/MS hydroxybenzoic acid and hydroxycinnamic acids showed a loss of CO2 and production of a [M-H-44] - fragment and as expected, the UV spectra of these two compounds were affected by their chemical structures. For flavonol and flavonol glycosides, the spectra of their glycosides and aglycones produced deprotonated [M-H]- and [A-H]- species, respectively, and their UV spectra each presented two major absorption peaks. The UV spectra and MS/MS data of flavan-3-ols and stilbenes were also investigated. Using the optimized LC/MS/MS analytical conditions, the phenolic extracts from six representative wine samples were analyzed and 31 phenolic compounds were detected, 26 of which were identified by searching the LC/UV and MS/MS libraries. Finally, the presence of phenolic compounds was confirmed in different wine samples using the LC/UV and LC/MS/MS libraries.

  16. Characterization of intact protein conjugates and biopharmaceuticals using ion-exchange chromatography with online detection by native electrospray ionization mass spectrometry and top-down tandem mass spectrometry.

    Science.gov (United States)

    Muneeruddin, Khaja; Nazzaro, Mark; Kaltashov, Igor A

    2015-10-06

    Characterization of biopharmaceutical products is a challenging task, which needs to be carried out at several different levels (including both primary structure and conformation). An additional difficulty frequently arises due to the structural heterogeneity inherent to many protein-based therapeutics (e.g., extensive glycosylation or "designer" modifications such as chemical conjugation) or introduced postproduction as a result of stress (e.g., oxidation and deamidation). A combination of ion-exchange chromatography (IXC) with online detection by native electrospray ionization mass spectrometry (ESI MS) allows characterization of complex and heterogeneous therapeutic proteins and protein conjugates to be accomplished at a variety of levels without compromising their conformational integrity. The IXC/ESI MS measurements allow protein conjugates to be profiled by analyzing conjugation stoichiometry and the presence of multiple positional isomers, as well as to establish the effect of chemical modifications on the conformational integrity of each species. While mass profiling alone is not sufficient for identification of nonenzymatic post-translational modifications (PTMs) that result in a very small mass change of the eluting species (e.g., deamidation), this task can be completed using online top-down structural analysis, as demonstrated using stressed interferon-β as an example. The wealth of information that can be provided by IXC/native ESI MS and tandem mass spectrometry (MS/MS) on protein-based therapeutics will undoubtedly make it a very valuable addition to the experimental toolbox of biopharmaceutical analysis.

  17. Mass spectrometry of hyper-velocity impacts of organic micrograins.

    Science.gov (United States)

    Srama, Ralf; Woiwode, Wolfgang; Postberg, Frank; Armes, Steven P; Fujii, Syuji; Dupin, Damien; Ormond-Prout, Jonathan; Sternovsky, Zoltan; Kempf, Sascha; Moragas-Klostermeyer, Georg; Mocker, Anna; Grün, Eberhard

    2009-12-01

    The study of hyper-velocity impacts of micrometeoroids is important for the calibration of dust sensors in space applications. For this purpose, submicron-sized synthetic dust grains comprising either polystyrene or poly[bis(4-vinylthiophenyl)sulfide] were coated with an ultrathin overlayer of an electrically conductive organic polymer (either polypyrrole or polyaniline) and were accelerated to speeds between 3 and 35 km s(-1) using the Heidelberg Dust Accelerator facility. Time-of-flight mass spectrometry was applied to analyse the resulting ionic impact plasma using a newly developed Large Area Mass Analyser (LAMA). Depending on the projectile type and the impact speed, both aliphatic and aromatic molecular ions and cluster species were identified in the mass spectra with masses up to 400 u. Clusters resulting from the target material (silver) and mixed clusters of target and projectile species were also observed. Impact velocities of between 10 and 35 km s(-1) are suitable for a principal identification of organic materials in micrometeoroids, whereas impact speeds below approximately 10 km s(-1) allow for an even more detailed analysis. Molecular ions and fragments reflect components of the parent molecule, providing determination of even complex organic molecules embedded in a dust grain. In contrast to previous measurements with the Cosmic Dust Analyser instrument, the employed LAMA instrument has a seven times higher mass resolution--approximately 200--which allowed for a detailed analysis of the complex mass spectra. These fundamental studies are expected to enhance our understanding of cometary, interplanetary and interstellar dust grains, which travel at similar hyper-velocities and are known to contain both aliphatic and aromatic organic compounds. Copyright 2009 John Wiley & Sons, Ltd.

  18. High Mass Accuracy and High Mass Resolving Power FT-ICR Secondary Ion Mass Spectrometry for Biological Tissue Imaging

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Donald F.; Kiss, Andras; Leach, Franklin E.; Robinson, Errol W.; Pasa-Tolic, Ljiljana; Heeren, Ronald M.

    2013-07-01

    Biological tissue imaging by secondary ion mass spectrometry has seen rapid development with the commercial availability of polyatomic primary ion sources. Endogenous lipids and other small bio-molecules can now be routinely mapped on the micrometer scale. Such experiments are typically performed on time-of-flight mass spectrometers for high sensitivity and high repetition rate imaging. However, such mass analyzers lack the mass resolving power to ensure separation of isobaric ions and the mass accuracy for exact mass elemental formula assignment. We have recently reported a secondary ion mass spectrometer with the combination of a C60 primary ion gun with a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) for high mass resolving power, high mass measurement accuracy and tandem mass spectrometry capabilities. In this work, high specificity and high sensitivity secondary ion FT-ICR MS was applied to chemical imaging of biological tissue. An entire rat brain tissue was measured with 150 μm spatial resolution (75 μm primary ion spot size) with mass resolving power (m/Δm50%) of 67,500 (at m/z 750) and root-mean-square measurement accuracy less than two parts-per-million for intact phospholipids, small molecules and fragments. For the first time, ultra-high mass resolving power SIMS has been demonstrated, with m/Δm50% > 3,000,000. Higher spatial resolution capabilities of the platform were tested at a spatial resolution of 20 μm. The results represent order of magnitude improvements in mass resolving power and mass measurement accuracy for SIMS imaging and the promise of the platform for ultra-high mass resolving power and high spatial resolution imaging.

  19. Mass Spectrometry-Based Detection and Assignment of Protein Posttranslational Modifications

    OpenAIRE

    Doll, S.; Burlingame, AL

    2014-01-01

    © 2014 American Chemical Society. Recent advances in mass spectrometry (MS)-based proteomics allow the identification and quantitation of thousands of posttranslational modification (PTM) sites in a single experiment. This follows from the development of more effective class enrichment strategies, new high performance instrumentation and bioinformatic algorithms with rigorous scoring strategies. More widespread use of these combined capabilities have led to a vast expansion in our knowledge o...

  20. Biomedical applications of accelerator mass spectrometry at ANU

    Energy Technology Data Exchange (ETDEWEB)

    Fifield, L.K.; Tada, M.L. di; Liu, K.; Cresswell, R.G. [Australian National University, Canberra, ACT (Australia). Department of Nuclear Physics; Day, J.P.; Oldham, C.L.; Popplewell, J.; Carson, R. [University of Manchester, (United Kingdom). Department of Chemistry

    1997-10-01

    Radioactive isotopic tracers are widely used in biomedical research, but for some elements of much current interest such as aluminium, silicon and plutonium, suitable isotopes for radioactive decay counting are not available. Each of these elements, however, possesses a long-lived isotope which could in principle be used if a suitable atom-counting detection technique were available. Accelerator Mass Spectrometry (AMS) is such a technique. AMS can provide ultra-sensitive detection of fewer than 10{sup 6} atoms of isotope, thereby enabling tracer experiments with human subjects without adding significantly to radiation body burdens. At the ANU, the AMS system based on the 14UD accelerator is being applied to a number of biomedical projects using {sup 26}AI, {sup 32}Si and the isotopes of plutonium as tracers

  1. Centrosome isolation and analysis by mass spectrometry-based proteomics

    DEFF Research Database (Denmark)

    Jakobsen, Lis; Schrøder, Jacob Morville; Larsen, Katja M

    2013-01-01

    Centrioles are microtubule-based scaffolds that are essential for the formation of centrosomes, cilia, and flagella with important functions throughout the cell cycle, in physiology and during development. The ability to purify centriole-containing organelles on a large scale, combined with advan......Centrioles are microtubule-based scaffolds that are essential for the formation of centrosomes, cilia, and flagella with important functions throughout the cell cycle, in physiology and during development. The ability to purify centriole-containing organelles on a large scale, combined...... with advances in protein identification using mass spectrometry-based proteomics, have revealed multiple centriole-associated proteins that are conserved during evolution in eukaryotes. Despite these advances, the molecular basis for the plethora of processes coordinated by cilia and centrosomes is not fully...

  2. Attomole quantitation of protein separations with accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Vogel, J S; Grant, P G; Buccholz, B A; Dingley, K; Turteltaub, K W

    2000-12-15

    Quantification of specific proteins depends on separation by chromatography or electrophoresis followed by chemical detection schemes such as staining and fluorophore adhesion. Chemical exchange of short-lived isotopes, particularly sulfur, is also prevalent despite the inconveniences of counting radioactivity. Physical methods based on isotopic and elemental analyses offer highly sensitive protein quantitation that has linear response over wide dynamic ranges and is independent of protein conformation. Accelerator mass spectrometry quantifies long-lived isotopes such as 14C to sub-attomole sensitivity. We quantified protein interactions with small molecules such as toxins, vitamins, and natural biochemicals at precisions of 1-5% . Micro-proton-induced-xray-emission quantifies elemental abundances in separated metalloprotein samples to nanogram amounts and is capable of quantifying phosphorylated loci in gels. Accelerator-based quantitation is a possible tool for quantifying the genome translation into proteome.

  3. Mass spectrometry analysis of gliadins in celiac disease.

    Science.gov (United States)

    Ferranti, Pasquale; Mamone, Gianfranco; Picariello, Gianluca; Addeo, Francesco

    2007-12-01

    In recent years, scientific research on wheat gluten proteins has followed three main directions aimed at (1) finding relationships between individual genetic alleles coding for gliadins, high or low molecular weight glutenin subunits, and the viscoelastic dough properties of flour-derived products such as pasta and bread; (2) identifying prolamins and derived peptides involved in celiac disease, a pathological condition in which the small intestine of genetically predisposed individuals is reversibly damaged; and (3) developing and validating sensitive and specific methods for detecting trace amounts of gluten proteins in gluten-free foods for celiac disease patients. In this review, the main aspects of current and perspective applications of mass spectrometry and proteomic technologies to the structural characterization of gliadins are presented, with focus on issues related to detection, identification, and quantification of intact gliadins, as well as gliadin-derived peptides relevant to the biochemical, immunological, and toxicological aspects of celiac disease.

  4. The Role of Mass Spectrometry in the "Omics" Era.

    Science.gov (United States)

    Di Girolamo, Francesco; Lante, Isabella; Muraca, Maurizio; Putignani, Lorenza

    2013-12-01

    Mass spectrometry (MS) is one of the key analytical technology on which the emerging ''-omics'' approaches are based. It may provide detection and quantization of thousands of proteins and biologically active metabolites from a tissue, body fluid or cell culture working in a ''global'' or ''targeted'' manner, down to ultra-trace levels. It can be expected that the high performance of MS technology, coupled to routine data handling, will soon bring fruit in the request for a better understanding of human diseases, leading to new molecular biomarkers, hence affecting drug targets and therapies. In this review, we focus on the main advances in the MS technologies, influencing genomics, transcriptomics, proteomics, lipidomics and metabolomics fields, up to the most recent MS applications to meta-omic studies.

  5. Monitoring the synthesis of biomolecules using mass spectrometry.

    Science.gov (United States)

    Miyagi, Masaru; Kasumov, Takhar

    2016-10-28

    The controlled and selective synthesis/clearance of biomolecules is critical for most cellular processes. In most high-throughput 'omics' studies, we measure the static quantities of only one class of biomolecules (e.g. DNA, mRNA, proteins or metabolites). It is, however, important to recognize that biological systems are highly dynamic in which biomolecules are continuously renewed and different classes of biomolecules interact and affect each other's production/clearance. Therefore, it is necessary to measure the turnover of diverse classes of biomolecules to understand the dynamic nature of biological systems. Herein, we explain why the kinetic analysis of a diverse range of biomolecules is important and how such an analysis can be done. We argue that heavy water ((2)H2O) could be a universal tracer for monitoring the synthesis of biomolecules on a global scale.This article is part of the themed issue 'Quantitative mass spectrometry'.

  6. Metallothionein dimers studied by nano-spray mass spectrometry.

    Science.gov (United States)

    Hathout, Yetrib; Reynolds, Kristy J; Szilagyi, Zoltan; Fenselau, Catherine

    2002-01-15

    Both transient and stable dimers of metallothionein have been characterized, based on earlier studies using NMR, circular dichroism and size-exclusion chromatography. Here additional characterization is provided by nanospray mass spectrometry. Rapid redistribution of metal ions between monomeric Cd7- and Zn7-metallothionein 2a is monitored by nanospray. An experiment in which theses two forms of the monomeric protein are separated by a dialysis membrane, which will pass metal ions but not proteins, confirms that a transient dimer must form for metal ions to be redistributed. On the other hand, size-exclusion chromatography of reconstituted Zn7- or Cd7-metallothionein revealed the presence of monomeric and dimeric species. These dimers do not equilibrate readily to form monomers and they are shown to be covalent.

  7. Evaluating plant immunity using mass spectrometry-based metabolomics workflows

    Science.gov (United States)

    Heuberger, Adam L.; Robison, Faith M.; Lyons, Sarah Marie A.; Broeckling, Corey D.; Prenni, Jessica E.

    2014-01-01

    Metabolic processes in plants are key components of physiological and biochemical disease resistance. Metabolomics, the analysis of a broad range of small molecule compounds in a biological system, has been used to provide a systems-wide overview of plant metabolism associated with defense responses. Plant immunity has been examined using multiple metabolomics workflows that vary in methods of detection, annotation, and interpretation, and the choice of workflow can significantly impact the conclusions inferred from a metabolomics investigation. The broad range of metabolites involved in plant defense often requires multiple chemical detection platforms and implementation of a non-targeted approach. A review of the current literature reveals a wide range of workflows that are currently used in plant metabolomics, and new methods for analyzing and reporting mass spectrometry (MS) data can improve the ability to translate investigative findings among different plant-pathogen systems. PMID:25009545

  8. Plant Phosphoproteomics: Analysis of Plasma Membrane Transporters by Mass Spectrometry

    DEFF Research Database (Denmark)

    Ye, Juanying; Rudashevskaya, Elena; Young, Clifford

    important physiological functions, such as stomata aperture, cell elongation, or cellular pH regulation. It is known that the activity of plant plasma membrane H+-ATPase is regulated by phosphorylation. Therefore, we first investigated the phosphorylation profile of plant H+-ATPase by enriching...... the phosphopeptides with optimized TiO2 and IMAC enrichment methods prior to MS analysis. We further investigated the global phosphorylation profile of the whole plant plasma membrane proteins using the combination of our recently established phosphopeptide enrichment method, Calcium phosphate precipitation......  Phosphorylation is a key regulatory factor in all aspects of eukaryotic biology including the regulation of plant membrane-bound transport proteins. To date, mass spectrometry (MS) has been introduced as powerful technology for study of post translational modifications (PTMs), including protein...

  9. Estimation of brassylic acid by gas chromatography-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Mohammed J. Nasrullah, Erica N. Pfarr, Pooja Thapliyal, Nicholas S. Dusek, Kristofer L. Schiele, Christy Gallagher-Lein, and James A. Bahr

    2010-10-29

    The main focus of this work is to estimate Brassylic Acid (BA) using gas chromatography-mass spectrometry (GC-MS). BA is a product obtained from the oxidative cleavage of Erucic Acid (EA). BA has various applications for making nylons and high performance polymers. BA is a 13 carbon compound with two carboxylic acid functional groups at the terminal end. BA has a long hydrocarbon chain that makes the molecule less sensitive to some of the characterization techniques. Although BA can be characterized by NMR, both the starting material (EA) and products BA and nonanoic acid (NA) have peaks at similar {delta}, ppm values. Hence it becomes difficult for the quick estimation of BA during its synthesis.

  10. Mass spectrometry imaging for visualizing organic analytes in food.

    Science.gov (United States)

    Handberg, Eric; Chingin, Konstantin; Wang, Nannan; Dai, Ximo; Chen, Huanwen

    2015-01-01

    The demand for rapid chemical imaging of food products steadily increases. Mass spectrometry (MS) is featured by excellent molecular specificity of analysis and is, therefore, a very attractive method for chemical profiling. MS for food imaging has increased significantly over the past decade, aided by the emergence of various ambient ionization techniques that allow direct and rapid analysis in ambient environment. In this article, the current status of food imaging with MSI is reviewed. The described approaches include matrix-assisted laser desorption/ionization (MALDI), but emphasize desorption atmospheric pressure photoionization (DAPPI), electrospray-assisted laser desorption/ionization (ELDI), probe electrospray ionization (PESI), surface desorption atmospheric pressure chemical ionization (SDAPCI), and laser ablation flowing atmospheric pressure afterglow (LA-FAPA). The methods are compared with regard to spatial resolution; analysis speed and time; limit of detection; and technical aspects. The performance of each method is illustrated with the description of a related application. Specific requirements in food imaging are discussed.

  11. Myofiber metabolic type determination by mass spectrometry imaging.

    Science.gov (United States)

    Centeno, Delphine; Vénien, Annie; Pujos-Guillot, Estelle; Astruc, Thierry; Chambon, Christophe; Théron, Laëtitia

    2017-08-01

    Matrix assisted laser desorption/ionization (MALDI) mass spectrometry imaging is a powerful tool that opens new research opportunities in the field of biology. In this work, predictive model was developed to discriminate metabolic myofiber types using the MALDI spectral data. Rat skeletal muscles are constituted of type I and type IIA fiber, which have an oxidative metabolism for glycogen degradation, and type IIX and type IIB fiber which have a glycolytic metabolism, present in different proportions according to the muscle function and physiological state. So far, myofiber type is determined by histological methods that are time consuming. Thanks to the predictive model, we were able to predict not only the metabolic fiber type but also their location, on the same muscle section that was used for MALDI imaging. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  12. Mass spectrometry imaging of plant metabolites--principles and possibilities.

    Science.gov (United States)

    Bjarnholt, Nanna; Li, Bin; D'Alvise, Janina; Janfelt, Christian

    2014-06-01

    Covering: up to the end of 2013 New mass spectrometry imaging (MSI) techniques are gaining importance in the analysis of plant metabolite distributions, and significant technological improvements have been introduced in the past decade. This review provides an introduction to the different MSI techniques and their applications in plant science. The most common methods for sample preparation are described, and the review also features a comprehensive table of published studies in MSI of plant material. A number of significant works are highlighted for their contributions to advance the understanding of plant biology through applications of plant metabolite imaging. Particular attention is given to the possibility for imaging of surface metabolites since this is highly dependent on the methods and techniques which are applied in imaging studies.

  13. Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry

    Science.gov (United States)

    Colizza, Kevin; Mahoney, Keira E.; Yevdokimov, Alexander V.; Smith, James L.; Oxley, Jimmie C.

    2016-11-01

    Efforts to analyze trace levels of cyclic peroxides by liquid chromatography/mass spectrometry gave evidence that acetonitrile suppressed ion formation. Further investigations extended this discovery to ketones, linear peroxides, esters, and possibly many other types of compounds, including triazole and menadione. Direct ionization suppression caused by acetonitrile was observed for multiple adduct types in both electrospray ionization and atmospheric pressure chemical ionization. The addition of only 2% acetonitrile significantly decreased the sensitivity of analyte response. Efforts to identify the mechanism were made using various nitriles. The ion suppression was reduced by substitution of an acetonitrile hydrogen with an electron-withdrawing group, but was exacerbated by electron-donating or steric groups adjacent to the nitrile. Although current theory does not explain this phenomenon, we propose that polar interactions between the various functionalities and the nitrile may be forming neutral aggregates that manifest as ionization suppression.

  14. Studies of Al metabolism in animal by accelerator mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    WangNa-Xiu; ZhuHan-Min; 等

    1997-01-01

    The correlation between Al metabolism and senile dementia in animal has been studied by AMS(accelerator mass spectrometry).Three groups of laboratory rats were fed with normal food.food with high Al content,and with enriched Ca and Mg together with high Al,respectively for six to eight months.Mapping test was made to recored th degree of wisdom degeneration.Half of the rats were sacrificed and Al contents in various organs were measured by atomic absorption spectroscopy.The rest were injected with 26Al,killed after 5,10,15,25,and 35d and 26Al contents measured by AMS.The distribution of Al as well as the correlation among the accumulation of 26Al,and the existed Al content and dementia was studied.

  15. A century of progress in molecular mass spectrometry.

    Science.gov (United States)

    McLafferty, Fred W

    2011-01-01

    The first mass spectrum of a molecule was measured by J.J. Thomson in 1910. Mass spectrometry (MS) soon became crucial to the study of isotopes and atomic weights and to the development of atomic weapons for World War II. Its notable applications to molecules began with the quantitative analysis of light hydrocarbons during World War II. When I joined the Dow Chemical Company in 1950, MS was not favored by organic chemists. This situation improved only with an increased understanding of gaseous ion chemistry, which was obtained through the use of extensive reference data. Gas chromatography-MS was developed in 1956, and tandem MS was first used a decade later. In neutralization-reionization MS, an unusual, unstable species is prepared by ion-beam neutralization and characterized by reionization. Electrospray ionization of a protein mixture produces its corresponding ionized molecules. In top-down proteomics, ions from an individual component can be mass separated and subjected to collision-activated and electron-capture dissociation to provide extensive sequence information.

  16. Combinatorial Labeling Method for Improving Peptide Fragmentation in Mass Spectrometry

    Science.gov (United States)

    Kuchibhotla, Bhanuramanand; Kola, Sankara Rao; Medicherla, Jagannadham V.; Cherukuvada, Swamy V.; Dhople, Vishnu M.; Nalam, Madhusudhana Rao

    2017-06-01

    Annotation of peptide sequence from tandem mass spectra constitutes the central step of mass spectrometry-based proteomics. Peptide mass spectra are obtained upon gas-phase fragmentation. Identification of the protein from a set of experimental peptide spectral matches is usually referred as protein inference. Occurrence and intensity of these fragment ions in the MS/MS spectra are dependent on many factors such as amino acid composition, peptide basicity, activation mode, protease, etc. Particularly, chemical derivatizations of peptides were known to alter their fragmentation. In this study, the influence of acetylation, guanidinylation, and their combination on peptide fragmentation was assessed initially on a lipase (LipA) from Bacillus subtilis followed by a bovine six protein mix digest. The dual modification resulted in improved fragment ion occurrence and intensity changes, and this resulted in the equivalent representation of b- and y-type fragment ions in an ion trap MS/MS spectrum. The improved representation has allowed us to accurately annotate the peptide sequences de novo. Dual labeling has significantly reduced the false positive protein identifications in standard bovine six peptide digest. Our study suggests that the combinatorial labeling of peptides is a useful method to validate protein identifications for high confidence protein inference. [Figure not available: see fulltext.

  17. Fast atom bombardment tandem mass spectrometry of carotenoids

    Energy Technology Data Exchange (ETDEWEB)

    van Breeman, R.B. [Univ. of Illinois, Chicago, IL (United States); Schmitz, H.H.; Schwartz, S.J. [North Carolina State Univ., Raleigh, NC (United States)

    1995-02-01

    Positive ion fast atom bombardment (FAB) tandem mass spectrometry (MS-MS) using a double-focusing mass spectrometer with linked scanning at constant B/E and high-energy collisionally activated dissociation (CAD) was used to differentiate 17 different cartenoids, including {beta}-apo-8{prime}- carotenal, astaxanthin, {alpha}-carotene, {beta}-carotene, {gamma}-carotene, {zeta}-carotene, canthaxanthin, {beta}-cryptoxanthin, isozeaxanthin bis (pelargonate), neoxanthin, neurosporene, nonaprene, lutein, lycopene, phytoene, phytofluene, and zeaxanthin. The carotenoids were either synthetic or isolated from plant tissues. The use of FAB ionization minimized degradation or rearrangement of the carotenoid structures due to the inherent thermal instability generally ascribed to these compounds. Instead of protonated molecules, both polar xanthophylls and nonpolar carotenes formed molecular ions, M{sup {center_dot}+}, during FAB ionization. Following collisionally activated dissociation, fragment ions of selected molecular ion precursors showed structural features indicative of the presence of hydroxyl groups, ring systems, ester groups, and aldehyde groups and the extent of aliphatic polyene conjugation. The fragmentation patterns observed in the mass spectra herein may be used as a reference for the structural determination of carotenoids isolated from plant and animal tissues. 18 refs., 4 figs.

  18. Determining in vivo phosphorylation sites using mass spectrometry.

    Science.gov (United States)

    Breitkopf, Susanne B; Asara, John M

    2012-04-01

    Phosphorylation is the most studied protein post-translational modification (PTM) in biological systems, since it controls cell growth, proliferation, survival, and other processes. High-resolution/high mass accuracy mass spectrometers are used to identify protein phosphorylation sites due to their speed, sensitivity, selectivity, and throughput. The protocols described here focus on two common strategies: (1) identifying phosphorylation sites from individual proteins and small protein complexes, and (2) identifying global phosphorylation sites from whole-cell and tissue extracts. For the first, endogenous or epitope-tagged proteins are typically immunopurified from cell lysates, purified via gel electrophoresis or precipitation, and enzymatically digested into peptides. Samples can be optionally enriched for phosphopeptides using immobilized metal affinity chromatography (IMAC) or titanium dioxide (TiO(2)) and then analyzed by microcapillary liquid chromatography/tandem mass spectrometry (LC-MS/MS). Global phosphorylation site analyses that capture pSer/pThr/pTyr sites from biological sources sites are more resource and time consuming and involve digesting the whole-cell lysate, followed by peptide fractionation by strong cation-exchange chromatography, phosphopeptide enrichment by IMAC or TiO(2), and LC-MS/MS. Alternatively, the protein lysate can be fractionated by SDS-PAGE, followed by digestion, phosphopeptide enrichment, and LC-MS/MS. One can also immunoprecipitate only phosphotyrosine peptides using a pTyr antibody followed by LC-MS/MS.

  19. Intraoperative tissue identification using rapid evaporative ionization mass spectrometry.

    Science.gov (United States)

    Balog, Júlia; Sasi-Szabó, László; Kinross, James; Lewis, Matthew R; Muirhead, Laura J; Veselkov, Kirill; Mirnezami, Reza; Dezső, Balázs; Damjanovich, László; Darzi, Ara; Nicholson, Jeremy K; Takáts, Zoltán

    2013-07-17

    Rapid evaporative ionization mass spectrometry (REIMS) is an emerging technique that allows near-real-time characterization of human tissue in vivo by analysis of the aerosol ("smoke") released during electrosurgical dissection. The coupling of REIMS technology with electrosurgery for tissue diagnostics is known as the intelligent knife (iKnife). This study aimed to validate the technique by applying it to the analysis of fresh human tissue samples ex vivo and to demonstrate the translation to real-time use in vivo in a surgical environment. A variety of tissue samples from 302 patients were analyzed in the laboratory, resulting in 1624 cancerous and 1309 noncancerous database entries. The technology was then transferred to the operating theater, where the device was coupled to existing electrosurgical equipment to collect data during a total of 81 resections. Mass spectrometric data were analyzed using multivariate statistical methods, including principal components analysis (PCA) and linear discriminant analysis (LDA), and a spectral identification algorithm using a similar approach was implemented. The REIMS approach differentiated accurately between distinct histological and histopathological tissue types, with malignant tissues yielding chemical characteristics specific to their histopathological subtypes. Tissue identification via intraoperative REIMS matched the postoperative histological diagnosis in 100% (all 81) of the cases studied. The mass spectra reflected lipidomic profiles that varied between distinct histological tumor types and also between primary and metastatic tumors. Thus, in addition to real-time diagnostic information, the spectra provided additional information on divergent tumor biochemistry that may have mechanistic importance in cancer.

  20. Electrospray ionisation mass spectrometry: principles and clinical applications.

    Science.gov (United States)

    Ho, C S; Lam, C W K; Chan, M H M; Cheung, R C K; Law, L K; Lit, L C W; Ng, K F; Suen, M W M; Tai, H L

    2003-01-01

    This mini-review provides a general understanding of electrospray ionisation mass spectrometry (ESI-MS) which has become an increasingly important technique in the clinical laboratory for structural study or quantitative measurement of metabolites in a complex biological sample. The first part of the review explains the electrospray ionisation process, design of mass spectrometers with separation capability, characteristics of the mass spectrum, and practical considerations in quantitative analysis. The second part then focuses on some clinical applications. The capability of ESI-tandem-MS in measuring bio-molecules sharing similar molecular structures makes it particularly useful in screening for inborn errors of amino acid, fatty acid, purine, pyrimidine metabolism and diagnosis of galactosaemia and peroxisomal disorders. Electrospray ionisation is also efficient in generating cluster ions for structural elucidation of macromolecules. This has fostered a new and improved approach (vs electrophoresis) for identification and quantification of haemoglobin variants. With the understanding of glycohaemoglobin structure, an IFCC reference method for glycohaemoglobin assay has been established using ESI-MS. It represents a significant advancement for the standardisation of HbA1c in diabetic monitoring. With its other applications such as in therapeutic drug monitoring, ESI-MS will continue to exert an important influence in the future development and organisation of the clinical laboratory service.