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Sample records for 252cf-plasma desorption mass

  1. Application of 252Cf plasma desorption mass spectrometry in dental research

    NASA Astrophysics Data System (ADS)

    Fritsch, Hans-Walter; Schmidt, Lothar; Köhl, Peter; Jungclas, Hartmut; Duschner, Heins

    1993-07-01

    Topically applied fluorides introduced in dental hygiene products elevate the concentration levels of fluoride in oral fluids and thus also affect chemical reactions of enamel de- and remineralisation. The chemical reactions on the surface of tooth enamel still are a subject of controversy. Here 252Cf-plasma desorption mass spectrometry and argon ion etching are used to analyse the molecular structure of the upper layes of enamel. The mass spectrum of untreated enamel is characterised by a series of cluster ions containing phosphate. It is evident that under certain conditions the molecular structure of the surface enamel is completely transformed by treatment with fluorides. The result of the degradation and precipitation processes is reflected by a total replacement of the phosphate by fluoride in the measured cluster ion distribution. Stepwise etching of the upper layers by Ar+ ions reveals the transition from a nearly pure CaF2 structure to the unchanged composition of the enamel mineral.

  2. Analusis by 252Cf plasma desorption mass spectrometry of Bordetella pertussis endotoxin after nitrous deamination

    NASA Astrophysics Data System (ADS)

    Deprun, C.; Karibian, D.; Caroff, M.

    1993-07-01

    Endotoxic lipopolysaccharides (LPSs) are the major components of Gram-negative bacterial outer membrane. Like many amphipathic molecules, they pose problems of heterogeneity, purity, solubility, and aggregation. Nevertheless, PDMS has recently have been applied to unmodified endotoxins composed of LPS having uip to five sugar units in their saccharide chain. The B. Pertussis LPSs, most of which have a dodecasaccharide domain, ahve been analysed by classical methods and the masses of the separate lipid and saccharide domains determined after rupture of the bond linking them. However, the acid treatment employed for these and most chemical analyses can also modify structures in the vicinity of the bond. In order to investigate this biologically-important region, the endotoxin was treated to nitrous deamination, which shortens the saccharide chain to five sugars, but preserves the acid-labile region of the LPS. The PDM spectrum of this derivative, which required new conditions for its desorption, confirmed the structure analysis and demonstrated the presence of at least four molecular species.

  3. Comparison of lipids A of several Salmonella and Escherichia strains by 252Cf plasma desorption mass spectrometry.

    PubMed Central

    Karibian, D; Deprun, C; Caroff, M

    1993-01-01

    Plasma desorption mass spectrometry has recently been used with success to characterize underivatized lipid A preparations: the major molecular species present give signals indicating their masses, from which probable compositions could be inferred by using the overall composition determined by chemical analyses. In the present study, plasma desorption mass spectrometry was used to compare structures in lipid A preparations isolated from several smooth and rough strains of Escherichia and Salmonella species. Preparations isolated from strains of both genera revealed considerable variation in degree of heterogeneity (number of fatty acids and presence or absence of hexadecanoic acid, phosphorylethanolamine, and aminoarabinose). Molecular species usually associated with Salmonella lipid A were found in preparations from Escherichia sp. In addition, preparations from three different batches of lipid A from one strain of Salmonella minnesota showed significant differences in composition. These results demonstrate that preparations used for biological and structural analyses should be defined in terms of their particular molecular constituents and that no generalizations based on analysis of a single preparation should be made. PMID:8491718

  4. Coal liquefaction process streams characterization and evaluation: The application of {sup 252}Cf-plasma desorption mass spectrometry to analysis of direct coal liquefaction heavy products

    SciTech Connect

    Larsen, J.W.; Lapucha, A.R.

    1992-10-01

    This study demonstrated the feasibility of using {sup 252}Cf PDMS, GPC, and MPLC for the examination of the tetrahydrofuran (THF)-soluble portion of distillation resid materials derived from direct coal liquefaction. The {sup 252}Cf-PDMS technique was used to determine molecular weight distributions of twenty-five THF-soluble resids. In order to detemine if {sup 252}Cf-PDMS responds differently to different chemical classes of compounds, Lehigh separated five of the samples into chemically distinct fractions by MPLC, then analyzed the parent samples, their fractions, and the re-mixed fractions by {sup 252}Cf-PDMS and GPC. Irreversible alteration of the samples upon separation was noted by Lehigh. This was confirmed by use of gas chromatographic (GC) analyses. The noted irreversible alterations prevented a direct comparison of the remixed materials and the original samples. Thus, the selective response of {sup 252}Cf-PDMS to different chemical classes of compounds could not be confirmed or ruled out. The number average molecular weights (M{sub n}) obtained by {sup 252}Cf-PDMS and GPC agreed well. However, the weight average molecular weights (M{sub w}) obtained by GPC are always higher than the corresponding {sup 252}Cf-PDMS results. Number average molecular weights and weight average molecular weights obtained with {sup 252}Cf-PDMS and GPC were compared with those obtained by field ionization mass spectrometry (FIMS), previously reported by SRI International for the parent resid samples from which the Lehigh THF-soluble samples were derived.

  5. Coal liquefaction process streams characterization and evaluation: The application of [sup 252]Cf-plasma desorption mass spectrometry to analysis of direct coal liquefaction heavy products

    SciTech Connect

    Larsen, J.W.; Lapucha, A.R.

    1992-10-01

    This study demonstrated the feasibility of using [sup 252]Cf PDMS, GPC, and MPLC for the examination of the tetrahydrofuran (THF)-soluble portion of distillation resid materials derived from direct coal liquefaction. The [sup 252]Cf-PDMS technique was used to determine molecular weight distributions of twenty-five THF-soluble resids. In order to detemine if [sup 252]Cf-PDMS responds differently to different chemical classes of compounds, Lehigh separated five of the samples into chemically distinct fractions by MPLC, then analyzed the parent samples, their fractions, and the re-mixed fractions by [sup 252]Cf-PDMS and GPC. Irreversible alteration of the samples upon separation was noted by Lehigh. This was confirmed by use of gas chromatographic (GC) analyses. The noted irreversible alterations prevented a direct comparison of the remixed materials and the original samples. Thus, the selective response of [sup 252]Cf-PDMS to different chemical classes of compounds could not be confirmed or ruled out. The number average molecular weights (M[sub n]) obtained by [sup 252]Cf-PDMS and GPC agreed well. However, the weight average molecular weights (M[sub w]) obtained by GPC are always higher than the corresponding [sup 252]Cf-PDMS results. Number average molecular weights and weight average molecular weights obtained with [sup 252]Cf-PDMS and GPC were compared with those obtained by field ionization mass spectrometry (FIMS), previously reported by SRI International for the parent resid samples from which the Lehigh THF-soluble samples were derived.

  6. [An improved method of preparing protein and peptide probes in mass spectrometry with ionization of division fragments by californium-252 (TOF-PDMS)].

    PubMed

    Chivanov, V D; Zubarev, R A; Aksenov, S A; Bordunova, O G; Eremenko, V I; Kabanets, V M; Tatarinova, V I; Mishnev, A K; Kuraev, V V; Knysh, A N; Eremenko, I A

    1996-08-01

    The addition of organic acids (picric, oxalic, citric, or tartaric) to peptide and protein samples was found to significantly increase the yield of their quasi-molecular ions (QMI) in time-of-flight 252Cf plasma desorption mass spectrometry. The yield of the ions depended on the pKa of the acid added.

  7. Combined liquid chromatography-mass spectrometry for trace analysis of pharmaceuticals

    NASA Astrophysics Data System (ADS)

    Schmidt, Lothar; Danigel, Harald; Jungclas, Hartmut

    1982-07-01

    A 252Cf-plasma desorption mass spectrometer (PDMS) for the analysis of thin layers from nonvolatile organic samples has been set up to be combined with a liquid chromatograph. A novel interface performs the direct inlet of the liquid sample through a capillary into the vacuum system of the spectrometer. Samples of drugs are periodically collected, transferred to the ion source and analysed using a rotating disk. This on-line sample preparation has been tested for three antiarrhythmic drugs using various solvents and mixtures.

  8. Plasma Desorption Mass Spectrometry: Coming of Age.

    ERIC Educational Resources Information Center

    Cotter, Robert J.

    1988-01-01

    Discusses the history and development of Plasma Desorption Mass Spectrometry to determine molecular weights and structures of proteins and polymers. Outlines theory, instrumentation, and sample preparation commonly used. Gives several examples of resulting spectra. (ML)

  9. Mass spectrometric peptide mapping analysis and structural characterization of dihydrodiol dehydrogenase isoenzymes.

    PubMed Central

    Gauss, C; Klein, J; Post, K; Suckau, D; Schneider, K; Thomas, H; Oesch, F; Przybylski, M

    1990-01-01

    The direct molecular weight determination and structural analysis of polypeptides and peptide mixtures have become amenable by the recent development of fast atom bombardment (FABMS) and 252Cf-plasma desorption (PDMS) mass spectrometry. FABMS and PDMS peptide mapping, i.e., the direct analysis of peptide mixtures resulting from proteolytic digestion, have been developed as powerful methods for the structural characterization of epoxide-metabolizing isoenzymes. The major advantage of this approach is provided by the selectivity of the endoproteolytic cleavage, combined with the specific and accurate molecular weight determination of complex digest mixtures containing peptides up to several thousands daltons in size. Furthermore, the mass spectrometric peptide mapping analysis can be combined with a range of protein-chemical modification reactions and with sequential degradation such as by carboxypeptidases. Both FABMS and PDMS peptide mapping have already been successfully applied to the structural differentiation of glutathione transferase and epoxide hydrolase isoenzymes in cases where references sequence data for at least one isoenzyme form was available. In the application described here, for a series of dihydrodiol dehydrogenase (DDH) isoenzymes with hitherto undetermined primary structures, a direct correlation between the structural differentiation from peptide mapping data and differences in their substrate specificities could be demonstrated. The mass spectrometric peptide mapping analysis of isoenzymes proved to be an efficient basis for the elucidation of the structure of one major DDH isoenzyme form; partial sequence data for this protein are reported. PMID:2272334

  10. Laser desorption mass spectrometry for biomolecule detection and its applications

    NASA Astrophysics Data System (ADS)

    Winston Chen, C. H.; Sammartano, L. J.; Isola, N. R.; Allman, S. L.

    2001-08-01

    During the past few years, we developed and used laser desorption mass spectrometry for biomolecule detections. Matrix-assisted laser desorption/ionization (MALDI) was successfully used to detect DNA fragments with the size larger than 3000 base pairs. It was also successfully used to sequence DNA with both enzymatic and chemical degradation methods to produce DNA ladders. We also developed MALDI with fragmentation for direct DNA sequencing for short DNA probes. Since laser desorption mass spectrometry for DNA detection has the advantages of fast speed and no need of labeling, it has a great potential for molecular diagnosis for disease and person identification by DNA fingerprinting. We applied laser desorption mass spectrometry to succeed in the diagnosis of cystic fibrosis and several other nerve degenerative diseases such as Huntington's disease. We also succeeded in demonstrating DNA typing for forensic applications.

  11. Charge Assisted Laser Desorption/Ionization Mass Spectrometry of Droplets

    PubMed Central

    Jorabchi, Kaveh; Westphall, Michael S.; Smith, Lloyd M.

    2008-01-01

    We propose and evaluate a new mechanism to account for analyte ion signal enhancement in ultraviolet-laser desorption mass spectrometry of droplets in the presence of corona ions. Our new insights are based on timing control of corona ion production, laser desorption, and peptide ion extraction achieved by a novel pulsed corona apparatus. We demonstrate that droplet charging rather than gas-phase ion-neutral reactions is the major contributor to analyte ion generation from an electrically isolated droplet. Implications of the new mechanism, termed charge assisted laser desorption/ionization (CALDI), are discussed and contrasted to those of the laser desorption atmospheric pressure chemical ionization method (LD-APCI). It is also demonstrated that analyte ion generation in CALDI occurs with external electric fields about one order of magnitude lower than those needed for atmospheric pressure matrix assisted laser desorption/ionization or electrospray ionization of droplets. PMID:18387311

  12. Desorption electrospray ionization-mass spectrometry of proteins

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Desorption electrospray ionization-mass spectrometry (DESI-MS) was evaluated for the detection of proteins ranging in molecular mass from 12 to 66 kDa. Proteins were uniformly deposited on a solid surface without pretreatment and analyzed with a DESI source coupled to a quadrupole ion trap mass spec...

  13. Desorption electrospray ionization mass spectrometry of intact bacteria

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Desorption electrospray ionization (DESI) mass spectrometry (MS) was used to differentiate 7 bacterial species based on their measured DESI-mass spectral profile. Both Gram positive and Gram negative bacteria were tested and included Escherichia coli, Staphyloccocus aureus, Enterococcus sp., Bordete...

  14. Quantitative matrix-assisted laser desorption/ionization mass spectrometry

    PubMed Central

    Roder, Heinrich; Hunsucker, Stephen W.

    2008-01-01

    This review summarizes the essential characteristics of matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry (TOF MS), especially as they relate to its applications in quantitative analysis. Approaches to quantification by MALDI-TOF MS are presented and published applications are critically reviewed. PMID:19106161

  15. Laser desorption in an ion trap mass spectrometer

    SciTech Connect

    Eiden, G.C.; Cisper, M.E.; Alexander, M.L.; Hemberger, P.H.; Nogar, N.S.

    1993-02-01

    Laser desorption in a ion-trap mass spectrometer shows significant promise for both qualitative and trace analysis. Several aspects of this methodology are discussed in this work. We previously demonstrated the generation of both negative and positive ions by laser desorption directly within a quadrupole ion trap. In the present work, we explore various combinations of d.c., r.f., and time-varying fields in order to optimize laser generated signals. In addition, we report on the application of this method to analyze samples containing compounds such as amines, metal complexes, carbon clusters, and polynuclear aromatic hydrocarbons. In some cases the ability to rapidly switch between positive and negative ion modes provides sufficient specificity to distinguish different compounds of a mixture with a single stage of mass spectrometry. In other experiments, we combined intensity variation studies with tandem mass spectrometry experiments and positive and negative ion detection to further enhance specificity.

  16. Laser desorption lamp ionization source for ion trap mass spectrometry.

    PubMed

    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. PMID:25601688

  17. Tissue Imaging Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Laskin, Julia; Heath, Brandi S.; Roach, Patrick J.; Cazares, Lisa H.; Semmes, O. John

    2012-01-03

    We present the first results showing the ambient imaging of biological samples in their native environment using nanospray desorption ionization (nanoDESI) mass spectrometry. NanoDESI is an ambient pressure ionization technique that enables precise control of ionization of molecules from substrates. We demonstrate highly sensitive and robust analysis of tissue samples with high spatial resolution (<12 {mu}m) without sample preparation, which will be essential for applications in clinical diagnostics, drug discovery, molecular biology, and biochemistry.

  18. Characterization of polymer decomposition products by laser desorption mass spectrometry

    NASA Technical Reports Server (NTRS)

    Pallix, Joan B.; Lincoln, Kenneth A.; Miglionico, Charles J.; Roybal, Robert E.; Stein, Charles; Shively, Jon H.

    1993-01-01

    Laser desorption mass spectrometry has been used to characterize the ash-like substances formed on the surfaces of polymer matrix composites (PMC's) during exposure on LDEF. In an effort to minimize fragmentation, material was removed from the sample surfaces by laser desorption and desorbed neutrals were ionized by electron impact. Ions were detected in a time-of-flight mass analyzer which allows the entire mass spectrum to be collected for each laser shot. The method is ideal for these studies because only a small amount of ash is available for analysis. Three sets of samples were studied including C/polysulfone, C/polyimide and C/phenolic. Each set contains leading and trailing edge LDEF samples and their respective controls. In each case, the mass spectrum of the ash shows a number of high mass peaks which can be assigned to fragments of the associated polymer. These high mass peaks are not observed in the spectra of the control samples. In general, the results indicate that the ash is formed from decomposition of the polymer matrix.

  19. Unexpected Analyte Oxidation during Desorption Electrospray Ionization - Mass Spectrometry

    SciTech Connect

    Pasilis, Sofie P; Kertesz, Vilmos; Van Berkel, Gary J

    2008-01-01

    During the analysis of surface spotted analytes using desorption electrospray ionization mass spectrometry (DESI-MS), abundant ions are sometimes observed that appear to be the result of oxygen addition reactions. In this investigation, the effect of sample aging, the ambient lab environment, spray voltage, analyte surface concentration, and surface type on this oxidative modification of spotted analytes, exemplified by tamoxifen and reserpine, during analysis by desorption electrospray ionization mass spectrometry was studied. Simple exposure of the samples to air and to ambient lighting increased the extent of oxidation. Increased spray voltage lead also to increased analyte oxidation, possibly as a result of oxidative species formed electrochemically at the emitter electrode or in the gas - phase by discharge processes. These oxidative species are carried by the spray and impinge on and react with the sampled analyte during desorption/ionization. The relative abundance of oxidized species was more significant for analysis of deposited analyte having a relatively low surface concentration. Increasing spray solvent flow rate and addition of hydroquinone as a redox buffer to the spray solvent were found to decrease, but not entirely eliminate, analyte oxidation during analysis. The major parameters that both minimize and maximize analyte oxidation were identified and DESI-MS operational recommendations to avoid these unwanted reactions are suggested.

  20. Counting Molecules by Desorption Ionization and Mass Spectrometry/Mass Spectrometry.

    ERIC Educational Resources Information Center

    Cooks, R. G.; Busch, K. L.

    1982-01-01

    Discusses two newer methods in mass spectrometry and shows how they can increase signal and signal-to-noise ratios, respectively. The first method, desorption ionization (DI), increases sensitivity while the second method, mass spectrometry/mass spectrometry (MS/MS), increases specificity. Together, the two methods offer improved analytical…

  1. The laser desorption/laser ionization mass spectra of some methylated xanthines and the laser desorption of caffeine and theophylline from thin layer chromatography plates

    NASA Astrophysics Data System (ADS)

    Rogers, Kevin; Milnes, John; Gormally, John

    1993-02-01

    Laser desorption/laser ionization time-of-flight mass spectra of caffeine, theophylline, theobromine and xanthine are reported. These mass spectra are compared with published spectra obtained using electron impact ionization. Mass spectra of caffeine and theophylline obtained by IR laser desorption from thin layer chromatography plates are also described. The laser desorption of materials from thin layer chromatography plates is discussed.

  2. Ion track structure probed by plasma desorption mass spectrometry

    NASA Astrophysics Data System (ADS)

    U. R. Sundqvist, Bo

    1993-07-01

    Since the discovery of plasma desorption mass spectrometry by Torgerson [D.F. Torgerson, R.P. Skowronski and R.D. Macfarlane, Biophys. Res. Commun., 60(1974) 616], the method has mainly been used in mass spectrometric studies of bioorganic molecules. However, the ejecta in this electronic sputtering process have also been studied with the aim to gain information on the structure of the ion track formed in a solid by the incident fission fragment. In this paper such studies will be described. In particular, the ejection of large whole ionised organic molecules and the synthesis of fullerenes at the impact of a fast heavy ion on an organic solid will be discussed. Those two processes are connected to different parts of the ion track. Also, the ejection of light ions and damage cross sections will be discussed and are shown to give additional information on the time and space evolution of energy deposited in a fast ion track.

  3. Laser Desorption Mass Spectrometry for DNA Sequencing and Analysis

    NASA Astrophysics Data System (ADS)

    Chen, C. H. Winston; Taranenko, N. I.; Golovlev, V. V.; Isola, N. R.; Allman, S. L.

    1998-03-01

    Rapid DNA sequencing and/or analysis is critically important for biomedical research. In the past, gel electrophoresis has been the primary tool to achieve DNA analysis and sequencing. However, gel electrophoresis is a time-consuming and labor-extensive process. Recently, we have developed and used laser desorption mass spectrometry (LDMS) to achieve sequencing of ss-DNA longer than 100 nucleotides. With LDMS, we succeeded in sequencing DNA in seconds instead of hours or days required by gel electrophoresis. In addition to sequencing, we also applied LDMS for the detection of DNA probes for hybridization LDMS was also used to detect short tandem repeats for forensic applications. Clinical applications for disease diagnosis such as cystic fibrosis caused by base deletion and point mutation have also been demonstrated. Experimental details will be presented in the meeting. abstract.

  4. Laser desorption mass spectrometry for point mutation detection

    SciTech Connect

    Taranenko, N.I.; Chung, C.N.; Zhu, Y.F.

    1996-10-01

    A point mutation can be associated with the pathogenesis of inherited or acquired diseases. Laser desorption mass spectrometry coupled with allele specific polymerase chain reaction (PCR) was first used for point mutation detection. G551D is one of several mutations of the cystic fibrosis transmembrane conductance regulator (CFTR) gene present in 1-3% of the mutant CFTR alleles in most European populations. In this work, two different approaches were pursued to detect G551D point mutation in the cystic fibrosis gene. The strategy is to amplify the desired region of DNA template by PCR using two primers that overlap one base at the site of the point mutation and which vary in size. If the two primers based on the normal sequence match the target DNA sequence, a normal PCR product will be produced. However, if the alternately sized primers that match the mutant sequence recognize the target DNA, an abnormal PCR product will be produced. Thus, the mass spectrometer can be used to identify patients that are homozygous normal, heterozygous for a mutation or homozygous abnormal at a mutation site. Another approach to identify similar mutations is the use of sequence specific restriction enzymes which respond to changes in the DNA sequence. Mass spectrometry is used to detect the length of the restriction fragments generated by digestion of a PCR generated target fragment. 21 refs., 10 figs., 2 tabs.

  5. Laser desorption mass spectrometry for point mutation detection

    SciTech Connect

    Taranenko, N.I.; Chung, C.N.; Zhu, Y.F.

    1996-12-31

    A point mutation can be associated with the pathogenesis of inherited or acquired diseases. Laser desorption mass spectrometry coupled with allele specific polymerase chain reaction (PCR) was first used for point mutation detection. G551D is one of several mutations of the cystic fibrosis transmembrane conductance regulator (CFTR) gene present in 1-3% of the mutant CFTR alleles in most European populations. In this work, two different approaches were pursued to detect G551D point mutation in the cystic fibrosis gene. The strategy is to amplify the desired region of DNA template by PCR using two primers that overlap one base at the site of the point mutation and which vary in size. If the two primers based on the normal sequence match the target DNA sequence, a normal PCR product will be produced. However, if the alternately sized primers that match the mutant sequence recognize the target DNA, an abnormal PCR product will be produced. Thus, the mass spectrometer can be used to identify patients that are homozygous normal, heterozygous for a mutation or homozygous abnormal at a mutation site. Another approach to identify similar mutations is the use of sequence specific restriction enzymes which respond to changes in the DNA sequence. Mass spectrometry is used to detect the length of the restriction fragments by digestion of a PCR generated target fragment. 21 refs., 10 figs., 2 tabs.

  6. Laser desorption studies of high mass biomolecules in Fourier-transform ion cyclotron resonance mass spectrometry.

    PubMed Central

    Solouki, T; Russell, D H

    1992-01-01

    Matrix-assisted laser desorption ionization is used to obtain Fourier-transform ion cyclotron resonance mass spectra of model peptides (e.g., gramicidin S, angiotensin I, renin substrate, melittin, and bovine insulin). Matrix-assisted laser desorption ionization yields ions having appreciable kinetic energies. Two methods for trapping the high kinetic energy ions are described: (i) the ion signal for [M+H]+ ions is shown to increase with increasing trapping voltages, and (ii) collisional relaxation is used for the detection of [M+H]+ ions of bovine insulin. Images PMID:1378614

  7. Multistage Reactive Transmission-Mode Desorption Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Peters, Kevin C.; Comi, Troy J.; Perry, Richard H.

    2015-09-01

    Elucidating reaction mechanisms is important for advancing many areas of science such as catalyst development. It is often difficult to probe fast reactions at ambient conditions with high temporal resolution. In addition, systems involving reagents that cross-react require analytical methods that can minimize interaction time and specify their order of introduction into the reacting system. Here, we explore the utility of transmission mode desorption electrospray ionization (TM-DESI) for reaction monitoring by directing a microdroplet spray towards a series of meshes with micrometer-sized openings coated with reagents, an approach we call multistage reactive TM-DESI (TM n -DESI, where n refers to the number of meshes; n = 2 in this report). Various stages of the reaction are initiated at each mesh surface, generating intermediates and products in microdroplet reaction vessels traveling towards the mass spectrometer. Using this method, we investigated the reactivity of iron porphyrin catalytic hydroxylation of propranolol and other substrates. Our experimental results indicate that TM n -DESI provides the ability to spatially separate reagents and control their order of introduction into the reacting system, thereby minimizing unwanted reactions that lead to catalyst deactivation and degradation products. In addition, comparison with DESI-MS analyses (the Zare and Latour laboratories published results suggesting accessible reaction times <1 ms) of the reduction of dichlorophenolindophenol by L-ascorbic acid suggest that TM 1 -DESI can access reaction times less than 1 ms. Multiple meshes allow sequential stages of desorption/ionization per MS scan, increasing the number of analytes and reactions that can be characterized in a single experiment.

  8. Imaging of Biological Tissues by Desorption Electrospray Ionization Mass Spectrometry

    PubMed Central

    Fernández, Facundo M.

    2013-01-01

    Mass spectrometry imaging (MSI) provides untargeted molecular information with the highest specificity and spatial resolution for investigating biological tissues at the hundreds to tens of microns scale. When performed under ambient conditions, sample pre-treatment becomes unnecessary, thus simplifying the protocol while maintaining the high quality of information obtained. Desorption electrospray ionization (DESI) is a spray-based ambient MSI technique that allows for the direct sampling of surfaces in the open air, even in vivo. When used with a software-controlled sample stage, the sample is rastered underneath the DESI ionization probe, and through the time domain, m/z information is correlated with the chemical species' spatial distribution. The fidelity of the DESI-MSI output depends on the source orientation and positioning with respect to the sample surface and mass spectrometer inlet. Herein, we review how to prepare tissue sections for DESI imaging and additional experimental conditions that directly affect image quality. Specifically, we describe the protocol for the imaging of rat brain tissue sections by DESI-MSI. PMID:23892773

  9. The laser desorption/laser ionization mass spectra of some indole derivatives and alkaloids

    NASA Astrophysics Data System (ADS)

    Rogers, Kevin; Milnes, John; Gormally, John

    1992-06-01

    The laser desorption and laser ionization mass spectra of some indole derivatives and alkaloids are described with particular reference to their modes of fragmentation. Mass spectra of yohimbine, reserpine, quinine and quinidine are presented. Full experimental details are given.

  10. CHARACTERIZATION OF CRYPTOSPORIDIUM PARVUM BY MATRIX-ASSISTED LASER DESORPTION -- IONIZATION TIME OF FLIGHT MASS SPECTROMETRY

    EPA Science Inventory

    Matrix assisted laser desorption/ionization (MALDI) mass spectrometry was used to investigate whole and freeze thawed Cryptosporidium parvum oocysts. Whole oocysts revealed some mass spectral features. Reproducible patterns of spectral markers and increased sensitivity were obtai...

  11. Solvent jet desorption capillary photoionization-mass spectrometry.

    PubMed

    Haapala, Markus; Teppo, Jaakko; Ollikainen, Elisa; Kiiski, Iiro; Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

    2015-03-17

    A new ambient mass spectrometry method, solvent jet desorption capillary photoionization (DCPI), is described. The method uses a solvent jet generated by a coaxial nebulizer operated at ambient conditions with nitrogen as nebulizer gas. The solvent jet is directed onto a sample surface, from which analytes are extracted into the solvent and ejected from the surface in secondary droplets formed in collisions between the jet and the sample surface. The secondary droplets are directed into the heated capillary photoionization (CPI) device, where the droplets are vaporized and the gaseous analytes are ionized by 10 eV photons generated by a vacuum ultraviolet (VUV) krypton discharge lamp. As the CPI device is directly connected to the extended capillary inlet of the MS, high ion transfer efficiency to the vacuum of MS is achieved. The solvent jet DCPI provides several advantages: high sensitivity for nonpolar and polar compounds with limit of detection down to low fmol levels, capability of analyzing small and large molecules, and good spatial resolution (250 μm). Two ionization mechanisms are involved in DCPI: atmospheric pressure photoionization, capable of ionizing polar and nonpolar compounds, and solvent assisted inlet ionization capable of ionizing larger molecules like peptides. The feasibility of DCPI was successfully tested in the analysis of polar and nonpolar compounds in sage leaves and chili pepper. PMID:25715054

  12. Laser desorption mass spectrometry for fast DNA analysis

    SciTech Connect

    Chen, C.H.; Ch`ang, L.Y.; Taranenko, N.I.; Allman, S.L.; Tang, K.; Matteson, K.J.

    1995-09-01

    During the past few years, major effort has been directed toward developing mass spectrometry to measure biopolymers because of the great potential benefit to biomedical research. Hellenkamp and his co-workers were the first to report that large polypeptide molecules can be ionized and detected without significant fragmentation when a greater number of nicotinic acid molecules are used as a matrix. This method is now well known as matrix-assisted laser desorption/ionization (MALDI). Since then, various groups have reported measurements of very large proteins by MALDI. Reliable protein analysis by MALDI is more or less well established. However, the application of MALDI to nucleic acids analysis has been found to be much more difficult. Most research on the measurement of nucleic acid by MALDI were stimulated by the Human Genome Project. Up to now, the only method for reliable routine analysis of nucleic acid is gel electrophoresis. Different sizes of nucleic acids can be separated in gel medium when a high electric field is applied to the gel. However, the time needed to separate different sizes of DNA segments usually takes from several minutes to several hours. If MALDI can be successfully used for nucleic acids analysis, the analysis time can be reduced to less than I millisecond. In addition, no tagging with radioactive materials or chemical dyes is needed. In this work, we will review recent progress related to MALDI for DNA analysis.

  13. Liquid Beam Ion Desorption Mass Spectrometry for Evaluating CASSINI Data

    NASA Astrophysics Data System (ADS)

    Stolz, Ferdinand; Reviol, Rene; Srama, Ralf; Trieloff, Mario; Postberg, Frank; Abel, Bernd

    2013-04-01

    Saturn's moon Enceladus emits plumes of ice particles from an area near its south pole which are detected and chemically analyzed by the Cosmic Dust Analyzer (CDA) on board the CASSINI spacecraft. Studying these ice particles provides unique insights into Enceladus geological properties. Technically the CDA is a time-of-flight mass spectrometer which delivers mass spectra of the particles and their fragments. Since interpretation of the available CDA data is particularly challenging we employ a laboratory experiment to imitate experimental conditions in space. Key part of our experimental setup is a micron-sized water beam in high vacuum. This beam is rapidly heated up by an infrared laser pulse, which is tuned to excite the OH-stretch vibration of water molecules. This causes the water beam to dissipate into small droplets, some of which carry a net charge even though the laser energy is well below the molecular ionisation energy. The charged droplets are then analyzed in a time-of-flight mass spectrometer. With this experimental setup we successfully simulated the space born ice particles measured at Enceladus. By varying the laser intensity in our experiments, we can vary the amount of energy deposited in the liquid beam, and thus model different particle velocities. Also, variation of solute concentration in the water beam provides valuable information about ice particle composition. Some examples for anorganic solutes studied so far are sodium chloride, ammonia and hydrogen sulfite. A special feature of our experimental technique is that desorption of particles from the liquid beam is particularly soft. This is explained by the fact that all laser energy is absorbed by the water molecules. In this way molecular bonds of solutes stay intact and molecular solutes are transferred into the droplet phase without getting destroyed. This is particularly interesting in the context of analyzing organic compounds - some of which have been detected at Enceladus. Using

  14. Desorption Mass Spectrometry for Nonvolatile Compounds Using an Ultrasonic Cutter

    NASA Astrophysics Data System (ADS)

    Habib, Ahsan; Ninomiya, Satoshi; Chen, Lee Chuin; Usmanov, Dilshadbek T.; Hiraoka, Kenzo

    2014-07-01

    In this work, desorption of nonvolatile analytes induced by friction was studied. The nonvolatile compounds deposited on the perfluoroalkoxy substrate were gently touched by an ultrasonic cutter oscillating with a frequency of 40 kHz. The desorbed molecules were ionized by a dielectric barrier discharge (DBD) ion source. Efficient desorption of samples such as drugs, pharmaceuticals, amino acids, and explosives was observed. The limits of detection for these compounds were about 1 ng. Many compounds were detected in their protonated forms without undergoing significant fragmentation. When the DBD was off, no ions for the neutral samples could be detected, meaning that only desorption along with little ionization took place by the present technique.

  15. Comparative mass spectrometric analyses of Photofrin oligomers by fast atom bombardment mass spectrometry, UV and IR matrix-assisted laser desorption/ionization mass spectrometry, electrospray ionization mass spectrometry and laser desorption/jet-cooling photoionization mass spectrometry.

    PubMed

    Siegel, M M; Tabei, K; Tsao, R; Pastel, M J; Pandey, R K; Berkenkamp, S; Hillenkamp, F; de Vries, M S

    1999-06-01

    Photofrin (porfimer sodium) is a porphyrin derivative used in the treatment of a variety of cancers by photodynamic therapy. This oligomer complex and a variety of porphyrin monomers, dimers and trimers were analyzed with five different mass spectral ionization techniques: fast atom bombardment, UV and IR matrix-assisted laser desorption/ionization, electrospray ionization, and laser desorption/jet-cooling photoionization. All five approaches resulted in very similar oligomer distributions with an average oligomer length of 2.7 +/- 0.1 porphyrin units. In addition to the Photofrin analysis, this study provides a side-by-side comparison of the spectra for the five different mass spectrometric techniques.

  16. A Combined Desorption Ionization by Charge Exchange (DICE) and Desorption Electrospray Ionization (DESI) Source for Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Chan, Chang-Ching; Bolgar, Mark S.; Miller, Scott A.; Attygalle, Athula B.

    2011-01-01

    A source that couples the desorption ionization by charge exchange (DICE) and desorption electrospray ionization (DESI) techniques together was demonstrated to broaden the range of compounds that can be analyzed in a single mass spectrometric experiment under ambient conditions. A tee union was used to mix the spray reagents into a partially immiscible blend before this mixture was passed through a conventional electrospray (ES) probe capillary. Using this technique, compounds that are ionized more efficiently by the DICE method and those that are ionized better with the DESI procedure could be analyzed simultaneously. For example, hydroquinone, which is not detected when subjected to DESI-MS in the positive-ion generation mode, or the sodium adduct of guaifenesin, which is not detected when examined by DICE-MS, could both be detected in one experiment when the two techniques were combined. The combined technique was able to generate the molecular ion, proton and metal adduct from the same compound. When coupled to a tandem mass spectrometer, the combined source enabled the generation of product ion spectra from the molecular ion and the [M + H]+ or [M + metal]+ ions of the same compound without the need to physically change the source from DICE to DESI. The ability to record CID spectra of both the molecular ion and adduct ions in a single mass spectrometric experiment adds a new dimension to the array of mass spectrometric methods available for structural studies.

  17. Spatially resolved thermal desorption/ionization coupled with mass spectrometry

    DOEpatents

    Jesse, Stephen; Van Berkel, Gary J; Ovchinnikova, Olga S

    2013-02-26

    A system and method for sub-micron analysis of a chemical composition of a specimen are described. The method includes providing a specimen for evaluation and a thermal desorption probe, thermally desorbing an analyte from a target site of said specimen using the thermally active tip to form a gaseous analyte, ionizing the gaseous analyte to form an ionized analyte, and analyzing a chemical composition of the ionized analyte. The thermally desorbing step can include heating said thermally active tip to above 200.degree. C., and positioning the target site and the thermally active tip such that the heating step forms the gaseous analyte. The thermal desorption probe can include a thermally active tip extending from a cantilever body and an apex of the thermally active tip can have a radius of 250 nm or less.

  18. Feasibility of desorption atmospheric pressure photoionization and desorption electrospray ionization mass spectrometry to monitor urinary steroid metabolites during pregnancy.

    PubMed

    Vaikkinen, Anu; Rejšek, Jan; Vrkoslav, Vladimír; Kauppila, Tiina J; Cvačka, Josef; Kostiainen, Risto

    2015-06-23

    Steroids have important roles in the progress of pregnancy, and their study in maternal urine is a non-invasive method to monitor the steroid metabolome and its possible abnormalities. However, the current screening techniques of choice, namely immunoassays and gas and liquid chromatography-mass spectrometry, do not offer means for the rapid and non-targeted multi-analyte studies of large sample sets. In this study, we explore the feasibility of two ambient mass spectrometry methods in steroid fingerprinting. Urine samples from pregnant women were screened by desorption electrospray ionization (DESI) and desorption atmospheric pressure photoionization (DAPPI) Orbitrap high resolution mass spectrometry (HRMS). The urine samples were processed by solid phase extraction for the DESI measurements and by enzymatic hydrolysis and liquid-liquid-extraction for DAPPI. Consequently, steroid glucuronides and sulfates were detected by negative ion mode DESI-HRMS, and free steroids by positive ion mode DAPPI-HRMS. In DESI, signals of eleven steroid metabolite ions were found to increase as the pregnancy proceeded, and in DAPPI ten steroid ions showed at least an order of magnitude increase during pregnancy. In DESI, the increase was seen for ions corresponding to C18 and C21 steroid glucuronides, while DAPPI detected increased excretion of C19 and C21 steroids. Thus both techniques show promise for the steroid marker screening in pregnancy.

  19. Surface-assisted laser desorption ionization mass spectrometry techniques for application in forensics.

    PubMed

    Guinan, Taryn; Kirkbride, Paul; Pigou, Paul E; Ronci, Maurizio; Kobus, Hilton; Voelcker, Nicolas H

    2015-01-01

    Matrix-assisted laser desorption ionization (MALDI) mass spectrometry (MS) is an excellent analytical technique for the rapid and sensitive analysis of macromolecules (>700 Da), such as peptides, proteins, nucleic acids, and synthetic polymers. However, the detection of smaller organic molecules with masses below 700 Da using MALDI-MS is challenging due to the appearance of matrix adducts and matrix fragment peaks in the same spectral range. Recently, nanostructured substrates have been developed that facilitate matrix-free laser desorption ionization (LDI), contributing to an emerging analytical paradigm referred to as surface-assisted laser desorption ionization (SALDI) MS. Since SALDI enables the detection of small organic molecules, it is rapidly growing in popularity, including in the field of forensics. At the same time, SALDI also holds significant potential as a high throughput analytical tool in roadside, work place and athlete drug testing. In this review, we discuss recent advances in SALDI techniques such as desorption ionization on porous silicon (DIOS), nano-initiator mass spectrometry (NIMS) and nano assisted laser desorption ionization (NALDI™) and compare their strengths and weaknesses with particular focus on forensic applications. These include the detection of illicit drug molecules and their metabolites in biological matrices and small molecule detection from forensic samples including banknotes and fingerprints. Finally, the review highlights recent advances in mass spectrometry imaging (MSI) using SALDI techniques.

  20. High-Speed Tandem Mass Spectrometric in Situ Imaging by Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Lanekoff, Ingela T.; Burnum-Johnson, Kristin E.; Thomas, Mathew; Short, Joshua TL; Carson, James P.; Cha, Jeeyeon; Dey, Sudhansu K.; Yang, Pengxiang; Prieto Conaway, Maria C.; Laskin, Julia

    2013-10-15

    Nanospray desorption electrospray ionization (nano-DESI) combined with tandem mass spectrometry (MS/MS), high-resolution mass analysis (m/m=17,500 at m/z 200), and rapid spectral acquisition enabled simultaneous imaging and identification of more than 300 molecules from 92 selected m/z windows (± 1 Da) with a spatial resolution of better than 150 um. Uterine sections of implantation sites on day 6 of pregnancy were analyzed in the ambient environment without any sample pre-treatment. MS/MS imaging was performed by scanning the sample under the nano-DESI probe at 10 um/s while acquiring higher-energy collision-induced dissociation (HCD) spectra for a targeted inclusion list of 92 m/z values at a rate of ~6.3 spectra/s. Molecular ions and their corresponding fragments, separated using high-resolution mass analysis, were assigned based on accurate mass measurement. Using this approach, we were able to identify and image both abundant and low-abundance isobaric species within each m/z window. MS/MS analysis enabled efficient separation and identification of isobaric sodium and potassium adducts of phospholipids. Furthermore, we identified several metabolites associated with early pregnancy and obtained the first 2D images of these molecules.

  1. Fossil fuel characterization using laser desorption mass spectrometry: Applications and limitations

    SciTech Connect

    Hunt, J.E.; Winans, R.E.

    1995-08-01

    Laser desorption mass spectroscopy (LDMS) and matrix-assisted laser desorption/ionization mass spectrometry (MALDI) are applicable to the high molecular weight compounds in fossil fuels which resist intact ionization. LD or MALDI of coals and extracts do not show reproducible ion intensity over mass 2000. This paper describes the scope and limitations of LD and MALD in time-of-flight mass spectrometers applied to high molecular weight molecules such as proteins and polymers. Coal was also analyzed. It is concluded that the sample preparation step is perhaps the most important part in MALDI. Observed high mass ions in coal may be from contaminant proteins. Optimal matrices must be found. Finally, the mass spectrum is senstive to number average molecular weight; a low value, however, does not preclude presence of high molecular weight species.

  2. Laser desorption time-of-flight mass spectrometer DNA analyzer. Final report

    SciTech Connect

    Chen, C.H.W.; Martin, S.A.

    1997-02-01

    The objective of this project is the development of a laser desorption time-of-flight mass spectrometer DNA analyzer which can be broadly used for biomedical research. Tasks include: pulsed ion extraction to improve resolution; two-component matrices to enhance ionization; and solid phase DNA purification.

  3. Identification of carbohydrates by matrix-free material-enhanced laser desorption/ionisation mass spectrometry.

    PubMed

    Hashir, Muhammad Ahsan; Stecher, Guenther; Bakry, Rania; Kasemsook, Saowapak; Blassnig, Bernhard; Feuerstein, Isabel; Abel, Gudrun; Popp, Michael; Bobleter, Ortwin; Bonn, Guenther K

    2007-01-01

    Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) is a sensitive mass spectrometric technique which utilises acidic materials as matrices for laser energy absorption, desorption and ionisation of analytes. These matrix materials produce background signals particularly in the low-mass range and make the detection and identification of small molecules difficult and nearly impossible. To overcome this problem this paper introduces matrix-free material-enhanced laser desorption/ionisation mass spectrometry (mf-MELDI-MS) for the screening and analysis of small molecules such as carbohydrates. For this purpose, 4,4'-azo-dianiline was immobilised on silica gel enabling the absorption of laser energy sufficient for successful desorption and ionisation of low molecular weight compounds. The particle and pore sizes, the solvent system for suspension and the sample preparation procedures have been optimised. The newly synthesised MELDI material delivered excellent spectra with regard to signal-to-noise ratio and detection sensitivity. Finally, wheat straw degradation products and Salix alba L. plant extracts were analysed proving the high performance and excellent behaviour of the introduced material.

  4. Laser Desorption Mass Spectrometry for High Throughput DNA Analysis and Its Applications

    SciTech Connect

    Allman, S.L.; Chen, C.H.; Golovlev, V.V.; Isola, N.R.; Matteson, K.J.; Potter, N.T.; Taranenko, N.I.

    1999-01-23

    Laser desorption mass spectrometry (LDMS) has been developed for DNA sequencing, disease diagnosis, and DNA Fingerprinting for forensic applications. With LDMS, the speed of DNA analysis can be much faster than conventional gel electrophoresis. No dye or radioactive tagging to DNA segments for detection is needed. LDMS is emerging as a new alternative technology for DNA analysis.

  5. Identification of Bacteria Using Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometry

    ERIC Educational Resources Information Center

    Kedney, Mollie G.; Strunk, Kevin B.; Giaquinto, Lisa M.; Wagner, Jennifer A.; Pollack, Sidney; Patton, Walter A.

    2007-01-01

    Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS or simply MALDI) has become ubiquitous in the identification and analysis of biomacromolecules. As a technique that allows for the molecular weight determination of otherwise nonvolatile molecules, MALDI has had a profound impact in the molecular…

  6. Laser desorption mass spectrometry for high-throughput DNA analysis and its applications

    NASA Astrophysics Data System (ADS)

    Chen, C. H. Winston; Golovlev, Valeri V.; Taranenko, N. I.; Allman, S. L.; Isola, Narayana R.; Potter, N. T.; Matteson, K. J.; Chang, Linus Y.

    1999-05-01

    Laser desorption mass spectrometry (LDMS) has been developed for DNA sequencing, disease diagnosis, and DNA fingerprinting for forensic applications. With LDMS, the speed of DNA analysis can be much faster than conventional gel electrophoresis. No dye or radioactive tagging to DNA segments for detection is needed. LDMS is emerging as a new alternative technology for DNA analysis.

  7. omniSpect: an open MATLAB-based tool for visualization and analysis of matrix-assisted laser desorption/ionization and desorption electrospray ionization mass spectrometry images.

    PubMed

    Parry, R Mitchell; Galhena, Asiri S; Gamage, Chaminda M; Bennett, Rachel V; Wang, May D; Fernández, Facundo M

    2013-04-01

    We present omniSpect, an open source web- and MATLAB-based software tool for both desorption electrospray ionization (DESI) and matrix-assisted laser desorption ionization (MALDI) mass spectrometry imaging (MSI) that performs computationally intensive functions on a remote server. These functions include converting data from a variety of file formats into a common format easily manipulated in MATLAB, transforming time-series mass spectra into mass spectrometry images based on a probe spatial raster path, and multivariate analysis. OmniSpect provides an extensible suite of tools to meet the computational requirements needed for visualizing open and proprietary format MSI data.

  8. Laser desorption mass spectrometry: Technical limitations, fundamentals, and application to coal

    SciTech Connect

    Hunt, J.E.; Winans, R.E.

    1995-12-31

    Objective of this study is to assess scope and limitations of laser desorption (LD) and matrix-assisted laser desorption (MALDI) as applied to coals. LD and MALDI mass spectrometry are increasingly used to detect intact molecular species, such as proteins with masses from 1000 to 100,000 amu and beyond. MALDI is also being used for high molecular weight polymers. A good example, related to coal-type systems, is the report on lignin mass spectrometry by MALDI. The mass spectrum shows a wide molecular distribution of several hundred to larger than 16000, with the center of gravity of the distribution around 2600. Results are interpreted in terms of oligomeric lignin molecules. Thus, if there are indeed large molecular species in a polymeric content in coals or coal extracts, MALDI is an attractive technique.

  9. The laser desorption/laser ionization mass spectra of some anti-inflammatory drugs

    NASA Astrophysics Data System (ADS)

    Milnes, John; Rogers, Kevin; Jones, Sian; Gormally, John

    1994-03-01

    The IR laser desorption/ultraviolet laser ionization time-of-flight mass spectra are reported for the anti-inflammatory drugs indomethacin, acemetacin, ibuprofen, flurbiprofen, diflunisal and mefenamic acid. It is found that the six compounds can be readily ionized by two photon absorption at a fixed wavelength of 266 nm. Mass spectra have been obtained under conditions of high ionizing irradiance and the observed fragmentation behaviour is discussed.

  10. Differential analysis of camphor wood products by desorption atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Zhu, Liang; Yan, Jianping; Zhu, Zhiqiang; Ouyang, Yongzhong; Zhang, Xinglei; Zhang, Wenjun; Dai, Ximo; Luo, Liping; Chen, Huanwen

    2013-01-23

    In the course of this study, desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS) was applied to readily acquire the mass spectral fingerprints of camphor wood and other wood samples under ambient conditions. Characteristic natural analytes, such as camphor and geraniol, were successfully detected in their protonated form and then identified by tandem mass spectrometry (MS(n)). Further principal component analysis (PCA) and cluster analysis (CA) of the mass spectrometric results allow a confident discrimination of camphor wood products from inferior/fake ones. These experimental findings demonstrate that DAPCI-MS is a valuable tool for differential analysis of untreated camphor wood products with sufficient sensitivity and high throughput.

  11. Matrix-assisted laser desorption fourier transform mass spectrometry for biological compounds

    SciTech Connect

    Hettich, R.; Buchanan, M.

    1990-01-01

    The recent development of matrix-assisted UV laser desorption (LD) mass spectrometry has made possible the ionization and detection of extremely large molecules (with molecular weights exceeding 100,000 Daltons). This technique has generated enormous interest in the biological community for the direct examination of large peptides and oligonucleotides. Although this matrix-assisted ionization method has been developed and used almost exclusively with time-of-flight (TOF) mass spectrometers, research is currently in progress to demonstrate this technique with trapped ion mass spectrometers, such as Fourier transform ion cyclotron resonance mass spectrometry (FTMS). The potential capabilities of FTMS for wide mass range, high resolution measurement, and ion trapping experiments suggest that this instrumental technique should be useful for the detailed structural characterization of large ions generated by the matrix-assisted technique. We have recently demonstrated that matrix-assisted ultraviolet laser desorption can be successfully used with FTMS for the ionization of small peptides. The objective of this report is to summarize the application and current limitations of matrix-assisted laser desorption FTMS for the characterization of peptides and oligonucleotides at the isomeric level. 4 refs., 3 figs., 2 tabs.

  12. Note: A versatile mass spectrometer chamber for molecular beam and temperature programmed desorption experiments.

    PubMed

    Tonks, James P; Galloway, Ewan C; King, Martin O; Kerherve, Gwilherm; Watts, John F

    2016-08-01

    A dual purpose mass spectrometer chamber capable of performing molecular beam scattering (MBS) and temperature programmed desorption (TPD) is detailed. Two simple features of this design allow it to perform these techniques. First, the diameter of entrance aperture to the mass spectrometer can be varied to maximize signal for TPD or to maximize angular resolution for MBS. Second, the mass spectrometer chamber can be radially translated so that it can be positioned close to the sample to maximize signal or far from the sample to maximize angular resolution. The performance of this system is described and compares well with systems designed for only one of these techniques.

  13. Note: A versatile mass spectrometer chamber for molecular beam and temperature programmed desorption experiments

    NASA Astrophysics Data System (ADS)

    Tonks, James P.; Galloway, Ewan C.; King, Martin O.; Kerherve, Gwilherm; Watts, John F.

    2016-08-01

    A dual purpose mass spectrometer chamber capable of performing molecular beam scattering (MBS) and temperature programmed desorption (TPD) is detailed. Two simple features of this design allow it to perform these techniques. First, the diameter of entrance aperture to the mass spectrometer can be varied to maximize signal for TPD or to maximize angular resolution for MBS. Second, the mass spectrometer chamber can be radially translated so that it can be positioned close to the sample to maximize signal or far from the sample to maximize angular resolution. The performance of this system is described and compares well with systems designed for only one of these techniques.

  14. Note: A versatile mass spectrometer chamber for molecular beam and temperature programmed desorption experiments.

    PubMed

    Tonks, James P; Galloway, Ewan C; King, Martin O; Kerherve, Gwilherm; Watts, John F

    2016-08-01

    A dual purpose mass spectrometer chamber capable of performing molecular beam scattering (MBS) and temperature programmed desorption (TPD) is detailed. Two simple features of this design allow it to perform these techniques. First, the diameter of entrance aperture to the mass spectrometer can be varied to maximize signal for TPD or to maximize angular resolution for MBS. Second, the mass spectrometer chamber can be radially translated so that it can be positioned close to the sample to maximize signal or far from the sample to maximize angular resolution. The performance of this system is described and compares well with systems designed for only one of these techniques. PMID:27587173

  15. Aerosol matrix-assisted laser desorption ionization for liquid chromatography/time-of-flight mass spectrometry

    SciTech Connect

    Murray, K.K.; Lewis, T.M.; Beeson, M.D.; Russell, D.H. )

    1994-05-15

    We report the application of aerosol matrix-assisted laser desorption ionization (MALDI) to liquid chromatography/mass spectrometry (LC/MS). The aerosol MALDI experiment uses aerosol liquid introduction in conjunction with pulsed UV laser ionization to form ions from large biomolecules in solution. Mass analysis is achieved in a time-of-flight mass spectrometer. In the LC/MALDI-MS experiment, the matrix solution is combined with the column effluent in a mixing tee, LC/MALDI-MS is demonstrated for the separation of bradykinin, gramicidin S, and myoglobin. 32 refs., 8 figs., 1 tab.

  16. Comparison of Three Plasma Sources for Ambient Desorption/Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    McKay, Kirsty; Salter, Tara L.; Bowfield, Andrew; Walsh, James L.; Gilmore, Ian S.; Bradley, James W.

    2014-09-01

    Plasma-based desorption/ionization sources are an important ionization technique for ambient surface analysis mass spectrometry. In this paper, we compare and contrast three competing plasma based desorption/ionization sources: a radio-frequency (rf) plasma needle, a dielectric barrier plasma jet, and a low-temperature plasma probe. The ambient composition of the three sources and their effectiveness at analyzing a range of pharmaceuticals and polymers were assessed. Results show that the background mass spectrum of each source was dominated by air species, with the rf needle producing a richer ion spectrum consisting mainly of ionized water clusters. It was also seen that each source produced different ion fragments of the analytes under investigation: this is thought to be due to different substrate heating, different ion transport mechanisms, and different electric field orientations. The rf needle was found to fragment the analytes least and as a result it was able to detect larger polymer ions than the other sources.

  17. Matrix-assisted laser desorption and electrospray ionization mass spectrometry of carminic acid isolated from cochineal

    NASA Astrophysics Data System (ADS)

    Maier, Marta S.; Parera, Sara D.; Seldes, Alicia M.

    2004-04-01

    Carminic acid, isolated from cochineal, was analyzed by matrix-assisted laser desorption/ionization (MALDI) and electrospray mass spectrometry (ESI-MS). Application of both techniques to the analysis of carminic acid suspended in linseed oil and applied to a piece of canvas, demonstrated the ability of MALDI and ESI-MS to identify this organic dye in a mixture as those used in easel painting.

  18. Thin-Layer Chromatography/Desorption Electrospray Ionization Mass Spectrometry: Investigation of Goldenseal Alkaloids

    SciTech Connect

    Van Berkel, Gary J; Tomkins, Bruce A; Kertesz, Vilmos

    2007-01-01

    Desorption electrospray ionization mass spectrometry was investigated as a means to qualitatively identify and to quantify analytes directly from developed normal-phase thin layer chromatography plates. The atmospheric sampling capillary of a commercial ion trap mass spectrometer was extended to permit sampling and ionization of analytes in bands separated on intact TLC plates (up to 10 cm x 10 cm). A surface positioning software package and the appropriate hardware enabled computer-controlled surface scanning along the length of development lanes or at fixed RF value across the plates versus the stationary desorption electrospray emitter. Goldenseal (Hydrastis canadensis) and related alkaloids and commercial dietary supplements were used as standards and samples. Alkaloid standards and samples were spotted and separated on aluminum- or glass-backed plates using established literature methods. The mass spectral signal levels as a function of desorption spray solvent were investigated with acetonitrile proving superior to methanol. The detection levels (ca. 5 ng each or 14 -28 pmol) in mass spectral full scan mode were determined statistically from the calibration curves (2.5 - 100 pmol) for the standards berberine, palmatine and hydrastinine spotted as a mixture and separated on the plates. Qualitative screening of the major alkaloids present in six different over-the-counter "goldenseal" dietary supplements was accomplished by obtaining full scan mass spectra during surface scans along the development lane in the direction of increasing RF value. In one sample, alkaloids were detected that strongly suggested the presence of at least one additional herb undeclared on the product label. These same data indicated the misidentification of one of the alkaloids in the TLC literature. Quantities of the alkaloids present in two of the samples determined using the mass spectral data were in reasonable agreement with the label values indicating the quantitative ability of

  19. Forensic applications of desorption electrospray ionisation mass spectrometry (DESI-MS).

    PubMed

    Morelato, Marie; Beavis, Alison; Kirkbride, Paul; Roux, Claude

    2013-03-10

    Desorption electrospray ionisation mass spectrometry (DESI-MS) is an emerging analytical technique that enables in situ mass spectrometric analysis of specimens under ambient conditions. It has been successfully applied to a large range of forensically relevant materials. This review assesses and highlights forensic applications of DESI-MS including the analysis and detection of illicit drugs, explosives, chemical warfare agents, inks and documents, fingermarks, gunshot residues and drugs of abuse in urine and plasma specimens. The minimal specimen preparation required for analysis and the sensitivity of detection achieved offer great advantages, especially in the field of forensic science.

  20. The Need for Speed in Matrix-Assisted Laser Desorption/Ionization Imaging Mass Spectrometry

    PubMed Central

    Prentice, Boone M.; Caprioli, Richard M.

    2016-01-01

    Imaging mass spectrometry (IMS) has emerged as a powerful analytical tool enabling the direct molecular mapping of many types of tissue. Specifically, matrix-assisted laser desorption/ ionization (MALDI) represents one of the most broadly applicable IMS technologies. In recent years, advances in solid state laser technology, mass spectrometry instrumentation, computer technology, and experimental methodology have produced IMS systems capable of unprecedented data acquisition speeds (>50 pixels/second). In applications of this technology, throughput is an important consideration when designing an IMS experiment. As IMS becomes more widely adopted, continual improvements in experimental setups will be important to address biologically and clinically relevant time scales. PMID:27570788

  1. Laser desorption/Fourier transform mass spectra of glycoalkaloids and steroid glycosides.

    PubMed

    Coates, M L; Wilkins, C L

    1986-04-01

    Positive- and negative-ion mass spectra of five glycoconjugates were obtained using laser desorption/Fourier transform mass spectrometry. These were the glycoalkaloids alpha-solanine and alpha-tomatine and the steroid glycosides gitoxin, lanatoside A and digitonin. Doping with KCl yielded both potassium- and chloride-attachment ions. Few fragment ions were observed for these species, with the exception of digitonin, although the negative-ion spectra showed relatively more fragmentation than the positive-ion spectra. All major fragments appeared to arise from losses of sugar groups due to cleavages at the glycosidic linkages. This contrasted sharply with the behavior of the malto-oligosaccharides studied in this laboratory.

  2. Detection and identification of immobilized low-volatility organophosphates by desorption ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Hagan, Nathan A.; Cornish, Timothy J.; Pilato, Robert S.; van Houten, Kelly A.; Antoine, Miquel D.; Lippa, Timothy P.; Becknell, Alan F.; Demirev, Plamen A.

    2008-12-01

    Two desorption ionization mass spectrometry (MS) techniques - ultraviolet laser desorption/ionization (LDI) and desorption electrospray ionization (DESI) - have been used to detect and identify low-volatility organophosphates when deposited on surfaces or loaded into the pore volume of porous inorganic or polymeric organic powders. The insecticides malathion and dicrotophos were chosen for this study as simulants of low vapor pressure chemical warfare agents which are inherently difficult to detect directly by traditional methods. Both liquid and powdered forms of either insecticide were readily detected by LDI or DESI MS. LDI MS was performed on a miniaturized home-built time-of-flight (TOF) mass spectrometer and a commercial TOF/TOF instrument. For DESI MS, a home-built ion source was interfaced to a commercial quadrupole ion trap. In LDI, intact molecular ion signatures could be acquired by using an appropriate cationizing agent and powder additive in positive ion mode. Tandem MS was used to confirm the identity of each analyte based on the observed characteristic fragmentation pattern. In DESI, less than 100 pg of the liquid insecticides spotted on clean surfaces were detected, while detection limits for the powder-loaded preparations were lower than 1 [mu]g. The effects of sample surface, salt additives, nanoparticle admixtures, and analyte solubility on the LDI and DESI MS sensitivity have been investigated as well.

  3. Pyroelectricity Assisted Infrared-Laser Desorption Ionization (PAI-LDI) for Atmospheric Pressure Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Li, Yanyan; Ma, Xiaoxiao; Wei, Zhenwei; Gong, Xiaoyun; Yang, Chengdui; Zhang, Sichun; Zhang, Xinrong

    2015-08-01

    A new atmospheric pressure ionization method termed pyroelectricity-assisted infrared laser desorption ionization (PAI-LDI) was developed in this study. The pyroelectric material served as both sample target plate and enhancing ionization substrate, and an IR laser with wavelength of 1064 nm was employed to realize direct desorption and ionization of the analytes. The mass spectra of various compounds obtained on pyroelectric material were compared with those of other substrates. For the five standard substances tested in this work, LiNbO3 substrate produced the highest ion yield and the signal intensity was about 10 times higher than that when copper was used as substrate. For 1-adamantylamine, as low as 20 pg (132.2 fmol) was successfully detected. The active ingredient in (Compound Paracetamol and 1-Adamantylamine Hydrochloride Capsules), 1-adamantylamine, can be sensitively detected at an amount as low as 150 pg, when the medicine stock solution was diluted with urine. Monosaccharide and oligosaccharides in Allium Cepa L. juice was also successfully identified with PAI-LDI. The method did not require matrix-assisted external high voltage or other extra facility-assisted set-ups for desorption/ionization. This study suggested exciting application prospect of pyroelectric materials in matrix- and electricity-free atmospheric pressure mass spectrometry research.

  4. Laser Desorption Ionization Mass Spectrometry Imaging of Drosophila Brain Using Matrix Sublimation versus Modification with Nanoparticles.

    PubMed

    Phan, Nhu T N; Mohammadi, Amir Saeid; Dowlatshahi Pour, Masoumeh; Ewing, Andrew G

    2016-02-01

    Laser desorption ionization mass spectrometry (LDI-MS) is used to image brain lipids in the fruit fly, Drosophila, a common invertebrate model organism in biological and neurological studies. Three different sample preparation methods, including sublimation with two common organic matrixes for matrix-assisted laser desorption ionization (MALDI) and surface-assisted laser desorption ionization (SALDI) using gold nanoparticles, are examined for sample profiling and imaging the fly brain. Recrystallization with trifluoroacetic acid following matrix deposition in MALDI is shown to increase the incorporation of biomolecules with one matrix, resulting in more efficient ionization, but not for the other matrix. The key finding here is that the mass fragments observed for the fly brain slices with different surface modifications are significantly different. Thus, these approaches can be combined to provide complementary analysis of chemical composition, particularly for the small metabolites, diacylglycerides, phosphatidylcholines, and triacylglycerides, in the fly brain. Furthermore, imaging appears to be beneficial using modification with gold nanoparticles in place of matrix in this application showing its potential for cellular and subcellular imaging. The imaging protocol developed here with both MALDI and SALDI provides the best and most diverse lipid chemical images of the fly brain to date with LDI. PMID:26705612

  5. Brominated Tyrosine and Polyelectrolyte Multilayer Analysis by Laser Desorption VUV Postionization and Secondary Ion Mass Spectrometry

    SciTech Connect

    University of Illinois at Chicago; Blaze, Melvin M. T.; Takahashi, Lynelle; Zhou, Jia; Ahmed, Musahid; Gasper, Gerald; Pleticha, F. Douglas; Hanley, Luke

    2011-03-14

    The small molecular analyte 3,5-dibromotyrosine (Br2Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br2Y were analyzed by laser desorption postionization mass spectrometry (LDPI-MS). LDPI-MS using 7.87 eV laser and tunable 8 ? 12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br2Y films allowed detection by≤8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br2Y to be ~;;8.3?0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at≤8 eV photon energies. However, single photon ionization could only detect Br2Y adsorbed within PEMs when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi3 + secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. The negative ion SIMS depended strongly on the high electron affinity of this specific analyte and the analyte?s condensed phase environment.

  6. In-Situ Organic Compound Analysis of the Meteorite Surface by Desorption Electrospray Ionization Coupled with an Orbitrap Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Naraoka, H.; Hashiguchi, M.

    2016-08-01

    It-situ analysis of organic compounds on the meteorite surface was performed by desorption electrospray ionization coupled with high resolution mass spectrometry. Indigenous peaks of meteorite origin were discriminated from the background.

  7. Fast Differential Analysis of Propolis Using Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry

    PubMed Central

    Huang, Xue-yong; Guo, Xia-li; Luo, Huo-lin; Fang, Xiao-wei; Zhu, Teng-gao; Zhang, Xing-lei; Chen, Huan-wen; Luo, Li-ping

    2015-01-01

    Mass spectral fingerprints of 24 raw propolis samples, including 23 from China and one from the United States, were directly obtained using surface desorption atmospheric pressure chemical ionization mass spectrometry (SDAPCI-MS) without sample pretreatment. Under the optimized experimental conditions, the most abundant signals were detected in the mass ranges of 70 to 500 m/z and 200 to 350 m/z, respectively. Principal component analyses (PCA) for the two mass ranges showed similarities in that the colors had a significant correlation with the first two PCs; in contrast there was no correlation with the climatic zones from which the samples originated. Analytes such as chrysin, pinocembrin, and quercetin were detected and identified using multiple stage mass spectrometry within 3 min. Therefore, SDAPCI-MS can be used for rapid and reliable high-throughput analysis of propolis. PMID:26339245

  8. Development of Laser Desorption Imaging Mass Spectrometry Methods to Investigate the Molecular Composition of Latent Fingermarks

    NASA Astrophysics Data System (ADS)

    Lauzon, Nidia; Dufresne, Martin; Chauhan, Vinita; Chaurand, Pierre

    2015-06-01

    For a century, fingermark analysis has been one of the most important and common methods in forensic investigations. Modern chemical analysis technologies have added the potential to determine the molecular composition of fingermarks and possibly identify chemicals a suspect may have come into contact with. Improvements in analytical detection of the molecular composition of fingermarks is therefore of great importance. In this regard, matrix-assisted laser desorption ionization (MALDI) and laser desorption ionization (LDI) imaging mass spectrometry (IMS) have proven to be useful technologies for fingermark analysis. In these analyses, the choice of ionizing agent and its mode of deposition are critical steps for the identification of molecular markers. Here we propose two novel and complementary IMS approaches for endogenous and exogenous substance detection in fingermarks: sublimation of 2-mercaptobenzothiazol (2-MBT) matrix and silver sputtering.

  9. Large Scale Nanoparticle Screening for Small Molecule Analysis in Laser Desorption Ionization Mass Spectrometry.

    PubMed

    Yagnik, Gargey B; Hansen, Rebecca L; Korte, Andrew R; Reichert, Malinda D; Vela, Javier; Lee, Young Jin

    2016-09-20

    Nanoparticles (NPs) have been suggested as efficient matrixes for small molecule profiling and imaging by laser-desorption ionization mass spectrometry (LDI-MS), but so far there has been no systematic study comparing different NPs in the analysis of various classes of small molecules. Here, we present a large scale screening of 13 NPs for the analysis of two dozen small metabolite molecules. Many NPs showed much higher LDI efficiency than organic matrixes in positive mode and some NPs showed comparable efficiencies for selected analytes in negative mode. Our results suggest that a thermally driven desorption process is a key factor for metal oxide NPs, but chemical interactions are also very important, especially for other NPs. The screening results provide a useful guideline for the selection of NPs in the LDI-MS analysis of small molecules. PMID:27573492

  10. Infrared matrix-assisted laser desorption electrospray ionization mass spectrometry imaging analysis of biospecimens.

    PubMed

    Bokhart, M T; Muddiman, D C

    2016-09-21

    Infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) mass spectrometry imaging (MSI) is a technique well suited for analysis of biological specimens. This tutorial review focuses on recent advancements and applications of IR-MALDESI MSI to better understand key biological questions. Through optimization of user-defined source parameters, comprehensive and quantitative MSI data can be obtained for a variety of analytes. The effect of an ice matrix layer is well defined in the context of desorption dynamics and resulting ion abundance. Optimized parameters and careful control of conditions affords quantitative MSI data which provides valuable information for targeted, label-free drug distribution studies and untargeted metabolomic datasets. Challenges and limitations of MSI using IR-MALDESI are addressed in the context of the bioimaging field. PMID:27484166

  11. Desorption electro-flow focusing ionization of explosives and narcotics for ambient pressure mass spectrometry.

    PubMed

    Forbes, Thomas P; Brewer, Tim M; Gillen, Greg

    2013-10-01

    Desorption electro-flow focusing ionization (DEFFI), a desorption-based ambient ion source, was developed, characterized, and evaluated as a possible source for field deployable ambient pressure mass spectrometry (APMS). DEFFI, based on an electro-flow focusing system, provides a unique configuration for the generation of highly charged energetic droplets for sample analysis and ionization. A concentrically flowing carrier gas focuses the liquid emanating from a capillary through a small orifice, generating a steady fluid jet. An electric field is applied across this jet formation region, producing high velocity charged droplets that impinge on an analyte laden surface. This configuration separates the jet charging region from the external environment, eliminating detrimental effects from droplet space charge or target surface charging. The sample desorption and ionization processes operate similar to desorption electrospray ionization (DESI). DEFFI demonstrated strong signal intensities and improved signal-to-noise ratios in both positive and negative mode mass spectrometry for narcotics, i.e., cocaine, and explosives, i.e., cyclotrimethylenetrinitramine (RDX), respectively. A characterization of DEFFI ionization mechanisms identified operation regimes of both electrospray and corona discharge based analyte ionization, as well as limitations in overall signal. In addition, the DEFFI response was directly compared to DESI-MS under similar operating conditions. This comparison established a wider and more stable optimal operating range, while requiring an order of magnitude lower applied gas pressure and applied potential for DEFFI than DESI. These reductions are due to the physical mode of jet formation and geometric configuration differences between DEFFI and DESI, pointing to a potential benefit of DEFFI-MS for field implementation.

  12. Manganese oxide nanoparticle-assisted laser desorption/ionization mass spectrometry for medical applications

    NASA Astrophysics Data System (ADS)

    Taira, Shu; Kitajima, Kenji; Katayanagi, Hikaru; Ichiishi, Eiichiro; Ichiyanagi, Yuko

    2009-06-01

    We prepared and characterized manganese oxide magnetic nanoparticles (d =5.6 nm) and developed nanoparticle-assited laser desorption/ionization (nano-PALDI) mass spectrometry. The nanoparticles had MnO2 and Mn2O3 cores conjugated with hydroxyl and amino groups, and showed paramagnetism at room temperature. The nanoparticles worked as an ionization assisting reagent in mass spectroscopy. The mass spectra showed no background in the low m/z. The nanoparticles could ionize samples of peptide, drug and proteins (approx. 5000 Da) without using matrix, i.e., 2,5-dihydroxybenzoic acid (DHB), 4-hydroxy-α-cinnamic acid (CHCA) and liquid matrix, as conventional ionization assisting reagents. Post source decay spectra by nano-PALDI mass spectrometry will yield information of the chemical structure of analytes.

  13. Direct Plant Tissue Analysis and Imprint Imaging by Desorption Electrospray Ionization Mass Spectrometry

    PubMed Central

    2011-01-01

    The ambient mass spectrometry technique, desorption electrospray ionization mass spectrometry (DESI-MS), is applied for the rapid identification and spatially resolved relative quantification of chlorophyll degradation products in complex senescent plant tissue matrixes. Polyfunctionalized nonfluorescent chlorophyll catabolites (NCCs), the “final” products of the chlorophyll degradation pathway, are detected directly from leaf tissues within seconds and structurally characterized by tandem mass spectrometry (MS/MS) and reactive-DESI experiments performed in situ. The sensitivity of DESI-MS analysis of these compounds from degreening leaves is enhanced by the introduction of an imprinting technique. Porous polytetrafluoroethylene (PTFE) is used as a substrate for imprinting the leaves, resulting in increased signal intensities compared with those obtained from direct leaf tissue analysis. This imprinting technique is used further to perform two-dimensional (2D) imaging mass spectrometry by DESI, producing well-resolved images of the spatial distribution of NCCs in senescent leaf tissues. PMID:21675752

  14. Probing silicon substitution in molecular sieves by plasma desorption mass spectrometry

    NASA Astrophysics Data System (ADS)

    Van Stipdonk, M. J.; von Heimburg, S. L.; Schweikert, E. A.

    1998-10-01

    Plasma desorption was used to produce secondary ion mass spectra from samples of unsubstituted and substituted aluminum phosphate materials. The yield of fingerprint ions representative of silicon oxide solids indicates that the incorporation of silicon into the material during synthesis and following calcination occurs via the formation of silicon-rich islands. Complementary X-ray photoelectron data provide supporting evidence that the surface of the substituted aluminum phosphate material becomes silicon rich and phosphorus depleted. No changes in the unsubstituted and substituted material with respect to composition and phase were detected using powder X-ray diffraction.

  15. Analysis of sexual assault evidence by desorption electrospray ionization mass spectrometry.

    PubMed

    Mirabelli, Mario F; Chramow, Alexander; Cabral, Elaine C; Ifa, Demian R

    2013-07-01

    Desorption electrospray ionization mass spectrometry (DESI-MS) is employed in the forensic analysis of chemical components present in condoms and imaging of latent fingerprints as circumstantial evidence of sexual assault. Polymers such as nonoxynol-9, polyethylene glycol, and polydimethylsiloxane, as well as small molecules additives such as N-methylmorpholine, N-octylamine, N,N-dibutyl formamide, and isonox 132, commonly used in lubricated condom formulations, were successfully characterized by DESI. The results suggest that DESI-MS is useful for identification of this type of evidence, and it has advantages over conventional extractive techniques, in terms of speed of analysis and ease of use. PMID:23832933

  16. Imaging of Proteins in Tissue Samples Using Nanospray Desorption Electrospray Ionization Mass Spectrometry.

    PubMed

    Hsu, Cheng-Chih; Chou, Pi-Tai; Zare, Richard N

    2015-11-17

    Chemical maps of tissue samples provide important information on biological processes therein. Recently, advances in tissue imaging have been achieved using ambient ionization techniques, such as desorption electrospray ionization mass spectrometry (DESI-MS), but such techniques have been almost exclusively confined to the mapping of lipids and metabolites. We report here the use of nanospray desorption electrospray ionization (nanoDESI) that allows us to image proteins in tissue samples in a label-free manner at atmospheric pressure with only minimum sample preparation. Multiply charged proteins with masses up to 15 kDa were successfully detected by nanoDESI using an LTQ Orbitrap mass spectrometer. In an adult mice brain section, expression of proteins including ubiquitin, β-thymosin, myelin basic protein, and hemoglobin were spatially mapped and characterized. We also determined the location of methylation on myelin basic protein. This imaging modality was further implemented to MYC-induced lymphomas. We observed an array of truncated proteins in the region where normal thymus cells were infiltrated by tumor cells, in contrast to healthy tissue.

  17. Removal of mercury contamination on primary mass standards by hydrogen plasma and thermal desorption

    NASA Astrophysics Data System (ADS)

    Fuchs, P.; Marti, K.; Russi, S.

    2013-02-01

    The removal of a high mercury contamination on a Pt reference mass by thermal desorption was studied directly by x-ray photoemission spectroscopy (XPS). Subsequently the contamination mechanism was investigated. Samples of PtIr and AuPt exposed to vapour of mercury in air were studied using XPS and gravimetric mass determination. We find an extremely rapid mercury contamination which takes place within minutes and reaches an initial equilibrium state after 2 h to 4 h. Roughly 1 to 2 monolayers of mercury adsorbs directly on the metal surface. A natural contamination of carbon and oxygen compounds is at the top. Due to the accumulation of mercury, we find a gain in mass which corresponds to 20 µg to 26 µg for a PtIr standard. XPS data from a historical Pt standard give strong evidence for further average mercury accumulation of (1.3 ± 0.1) µg/year during a period of more than a century. This can be explained by a two-step mechanism presented in this study. The speed of contamination depends on the initial surface conditions. Polishing activates the surface and results in an enhanced accumulation of mercury. Natural contamination by C and O can delay but not prevent contamination. We further demonstrate that the mercury contamination can be removed by both hydrogen plasma and thermal desorption. The removal of mercury by hydrogen plasma can directly be attributed to the synthesis of gaseous mercury dihydrides at low pressures.

  18. Identification of Microalgae by Laser Desorption/Ionization Mass Spectrometry Coupled with Multiple Nanomatrices.

    PubMed

    Peng, Lung-Hsiang; Unnikrishnan, Binesh; Shih, Chi-Yu; Hsiung, Tung-Ming; Chang, Jeng; Hsu, Pang-Hung; Chiu, Tai-Chia; Huang, Chih-Ching

    2016-04-01

    In this study, we demonstrate a simple method to identify microalgae by surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) using three different substrates: HgSe, HgTe, and HgTeSe nanostructures. The fragmentation/ionization processes of complex molecules in algae varied according to the heat absorption and transfer efficiency of the nanostructured matrices (NMs). Therefore, the mass spectra obtained for microalgae showed different patterns of m/z values for different NMs. The spectra contained both significant and nonsignificant peaks. Constructing a Venn diagram with the significant peaks obtained for algae when using HgSe, HgTe, and HgTeSe NMs in m/z ratio range 100-1000, a unique relationship among the three sets of values was obtained. This unique relationship of sets is different for each species of microalgae. Therefore, by observing the particular relationship of sets, we successfully identified different algae such as Isochrysis galbana, Emiliania huxleyi, Thalassiosira weissflogii, Nannochloris sp., Skeletonema cf. costatum, and Tetraselmis chui. This simple and cost-effective SALDI-MS analysis method coupled with multi-nanomaterials as substrates may be extended to identify other microalgae and microorganisms in real samples. Graphical Abstract Identification of microalgae by surface-assisted laser desorption/ionization mass spectrometry coupled with three different mercury-based nanosubstrates. PMID:26842733

  19. Laser desorption/ionization mass spectrometry of lipids using etched silver substrates.

    PubMed

    Schnapp, Andreas; Niehoff, Ann-Christin; Koch, Annika; Dreisewerd, Klaus

    2016-07-15

    Silver-assisted laser desorption/ionization mass spectrometry can be used for the analysis of small molecules. For example, adduct formation with silver cations enables the molecular analysis of long-chain hydrocarbons, which are difficult to ionize via conventional matrix-assisted laser desorption ionization (MALDI). Here we used highly porous silver foils, produced by etching with nitric acid, as sample substrates for LDI mass spectrometry. As model system for the analysis of complex lipid mixtures, cuticular extracts of fruit flies (Drosophila melanogaster) and worker bees (Apis mellifera) were investigated. The mass spectra obtained by spotting extract onto the etched silver substrates demonstrate the sensitive detection of numerous lipid classes such as long-chain saturated and unsaturated hydrocarbons, fatty acyl alcohols, wax esters, and triacylglycerols. MS imaging of cuticular surfaces with a lateral resolution of a few tens of micrometers became possible after blotting, i.e., after transferring lipids by physical contact with the substrate. The examples of pheromone-producing male hindwings of the squinting bush brown butterfly (Bicyclus anynana) and a fingermark are shown. Because the substrates are also easy to produce, they provide a viable alternative to colloidal silver nanoparticles and other so far described silver substrates.

  20. Laser Desorption Postionization Mass Spectrometry of Antibiotic-Treated Bacterial Biofilms using Tunable Vacuum Ultraviolet Radiation

    SciTech Connect

    Gasper, Gerald L; Takahashi, Lynelle K; Zhou, Jia; Ahmed, Musahid; Moore, Jerry F; Hanley, Luke

    2010-08-04

    Laser desorption postionization mass spectrometry (LDPI-MS) with 8.0 ? 12.5 eV vacuum ultraviolet synchrotron radiation is used to single photon ionize antibiotics andextracellular neutrals that are laser desorbed both neat and from intact bacterial biofilms. Neat antibiotics are optimally detected using 10.5 eV LDPI-MS, but can be ionized using 8.0 eV radiation, in agreement with prior work using 7.87 eV LDPI-MS. Tunable vacuum ultraviolet radiation also postionizes laser desorbed neutrals of antibiotics and extracellular material from within intact bacterial biofilms. Different extracellular material is observed by LDPI-MS in response to rifampicin or trimethoprim antibiotic treatment. Once again, 10.5 eV LDPI-MS displays the optimum trade-off between improved sensitivity and minimum fragmentation. Higher energy photons at 12.5 eV produce significant parent ion signal, but fragment intensity and other low mass ions are also enhanced. No matrix is added to enhance desorption, which is performed at peak power densities insufficient to directly produce ions, thus allowing observation of true VUV postionization mass spectra of antibiotic treated biofilms.

  1. Imaging of Lipids and Metabolites Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Lanekoff, Ingela; Laskin, Julia

    2015-01-17

    In recent years, mass spectroscopy imaging (MSI) has emerged as a foundational technique in metabolomics and drug screening providing deeper understanding of complex mechanistic pathways within biochemical systems and biological organisms. We have been invited to contribute a chapter to a new Springer series volume, entitled “Mass Spectrometry Imaging of Small Molecules”. The volume is planned for the highly successful lab protocol series Methods in Molecular Biology, published by Humana Press, USA. The volume is aimed to equip readers with step-by-step mass spectrometric imaging protocols and bring rapidly maturing methods of MS imaging to life science researchers. The chapter will provide a detailed protocol of ambient MSI by use of nanospray desorption electrospray ionization.

  2. Trace level detection of explosives in solution using leidenfrost phenomenon assisted thermal desorption ambient mass spectrometry.

    PubMed

    Saha, Subhrakanti; Mandal, Mridul Kanti; Chen, Lee Chuin; Ninomiya, Satoshi; Shida, Yasuo; Hiraoka, Kenzo

    2013-01-01

    The present paper demonstrates the detection of explosives in solution using thermal desorption technique at a temperature higher than Leidenfrost temperature of the solvent in combination with low temperature plasma (LTP) ionization. Leidenfrost temperature of a solvent is the temperature above which the solvent droplet starts levitation instead of splashing when placed on a hot metallic surface. During this desorption process, slow and gentle solvent evaporation takes place, which leads to the pre-concentration of less-volatile explosive molecules in the droplet and the explosive molecules are released at the last moment of droplet evaporation. The limits of detection for explosives studied by using this thermal desorption LTP ionization method varied in a range of 1 to 10 parts per billion (ppb) using a droplet volume of 20 μL (absolute sample amount 90-630 fmol). As LTP ionization method was applied and ion-molecule reactions took place in ambient atmosphere, various ion-molecule adduct species like [M+NO2](-), [M+NO3](-), [M+HCO3](-), [M+HCO4](-) were generated together with [M-H](-) peak. Each peak was unambiguously identified using 'Exactive Orbitrap' mass spectrometer in negative ionization mode within 3 ppm deviation compared to its exact mass. This newly developed technique was successfully applied to detect four explosives contained in the pond water and soil sample with minor sample pre-treatment and the explosives were detected with ppb levels. The present method is simple, rapid and can detect trace levels of explosives with high specificity from solutions. PMID:24349927

  3. Trace Level Detection of Explosives in Solution Using Leidenfrost Phenomenon Assisted Thermal Desorption Ambient Mass Spectrometry

    PubMed Central

    Saha, Subhrakanti; Mandal, Mridul Kanti; Chen, Lee Chuin; Ninomiya, Satoshi; Shida, Yasuo; Hiraoka, Kenzo

    2013-01-01

    The present paper demonstrates the detection of explosives in solution using thermal desorption technique at a temperature higher than Leidenfrost temperature of the solvent in combination with low temperature plasma (LTP) ionization. Leidenfrost temperature of a solvent is the temperature above which the solvent droplet starts levitation instead of splashing when placed on a hot metallic surface. During this desorption process, slow and gentle solvent evaporation takes place, which leads to the pre-concentration of less-volatile explosive molecules in the droplet and the explosive molecules are released at the last moment of droplet evaporation. The limits of detection for explosives studied by using this thermal desorption LTP ionization method varied in a range of 1 to 10 parts per billion (ppb) using a droplet volume of 20 μL (absolute sample amount 90–630 fmol). As LTP ionization method was applied and ion–molecule reactions took place in ambient atmosphere, various ion–molecule adduct species like [M+NO2]−, [M+NO3]−, [M+HCO3]−, [M+HCO4]− were generated together with [M−H]− peak. Each peak was unambiguously identified using ‘Exactive Orbitrap’ mass spectrometer in negative ionization mode within 3 ppm deviation compared to its exact mass. This newly developed technique was successfully applied to detect four explosives contained in the pond water and soil sample with minor sample pre-treatment and the explosives were detected with ppb levels. The present method is simple, rapid and can detect trace levels of explosives with high specificity from solutions. PMID:24349927

  4. Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography.

    PubMed

    Winter, Gregory T; Wilhide, Joshua A; LaCourse, William R

    2016-02-01

    Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot. PMID:26471042

  5. Laser desorption time-of-flight mass spectrometry of vacuum UV photo-processed methanol ice

    NASA Astrophysics Data System (ADS)

    Paardekooper, D. M.; Bossa, J.-B.; Linnartz, H.

    2016-07-01

    Context. Methanol in the interstellar medium mainly forms upon sequential hydrogenation of solid CO. With typical abundances of up to 15% (with respect to water) it is an important constituent of interstellar ices where it is considered as a precursor in the formation of large and complex organic molecules (COMs), e.g. upon vacuum UV (VUV) photo-processing or exposure to cosmic rays. Aims: This study aims at detecting novel complex organic molecules formed during the VUV photo-processing of methanol ice in the laboratory using a technique more sensitive than regular surface diagnostic tools. In addition, the formation kinetics of the main photo-products of methanol are unravelled for an astronomically relevant temperature (20 K) and radiation dose. Methods: The VUV photo-processing of CH3OH ice is studied by applying laser desorption post-ionisation time-of-flight mass spectrometry (LDPI TOF-MS), and analysed by combining molecule-specific fragmentation and desorption features. Results: The mass spectra correspond to fragment ions originating from a number of previously recorded molecules and from new COMs, such as the series (CO)xH, with x = 3 and y < 3x-1, to which prebiotic glycerin belongs. The formation of these large COMs has not been reported in earlier photolysis studies and suggests that such complex species may form in the solid state under interstellar conditions.

  6. Revisiting the quantitative features of surface-assisted laser desorption/ionization mass spectrometric analysis.

    PubMed

    Wu, Ching-Yi; Lee, Kai-Chieh; Kuo, Yen-Ling; Chen, Yu-Chie

    2016-10-28

    Surface-assisted laser desorption/ionization (SALDI) coupled with mass spectrometry (MS) is frequently used to analyse small organics owing to its clean background. Inorganic materials can be used as energy absorbers and the transfer medium to facilitate the desorption/ionization of analytes; thus, they are used as SALDI-assisting materials. Many studies have demonstrated the usefulness of SALDI-MS in quantitative analysis of small organics. However, some characteristics occurring in SALDI-MS require certain attention to ensure the reliability of the quantitative analysis results. The appearance of a coffee-ring effect in SALDI sample preparation is the primary factor that can affect quantitative SALDI-MS analysis results. However, to the best of our knowledge, there are no reports relating to quantitative SALDI-MS analysis that discuss or consider this effect. In this study, the coffee-ring effect is discussed using nanoparticles and nanostructured substrates as SALDI-assisting materials to show how this effect influences SALDI-MS analysis results. Potential solutions for overcoming the existing problems are also suggested.This article is part of the themed issue 'Quantitative mass spectrometry'.

  7. Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography

    NASA Astrophysics Data System (ADS)

    Winter, Gregory T.; Wilhide, Joshua A.; LaCourse, William R.

    2016-02-01

    Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot.

  8. Laser desorption mass spectrometry and small angle neutron scattering of heavy fossil materials

    SciTech Connect

    Hunt, J.E.; Winans, R.E.; Thiyagarajan, P.

    1997-09-01

    The determination of the structural building blocks and the molecular weight range of heavy hydrocarbon materials is of crucial importance in research on their reactivity and for their processing. The chemically and physically heterogenous nature of heavy hydrocarbon materials, such as coals, heavy petroleum fractions, and residues, dictates that their structure and reactivity patterns be complicated. The problem is further complicated by the fact that the molecular structure and molecular weight distribution of these materials is not dependent on a single molecule, but on a complex mixture of molecules which vary among coals and heavy petroleum samples. Laser Desorption mass spectrometry (LDMS) is emerging as a technique for molecular weight determination having found widespread use in biological polymer research, but is still a relatively new technique in the fossil fuel area. Small angle neutron scattering (SANS) provides information on the size and shape of heavy fossil materials. SANS offers the advantages of high penetration power even in thick cells at high temperatures and high contrast for hydrocarbon systems dispersed in deuterated solvents. LDMS coupled with time of flight has the advantages of high sensitivity and transmission and high mass range. We have used LDMS to examine various heavy fossil-derived materials including: long chain hydrocarbons, asphaltenes from petroleum vacuum resids, and coals. This paper describes the application of laser desorption and small angle neutron scattering techniques to the analysis of components in coals, petroleum resids and unsaturated polymers.

  9. Revisiting the quantitative features of surface-assisted laser desorption/ionization mass spectrometric analysis.

    PubMed

    Wu, Ching-Yi; Lee, Kai-Chieh; Kuo, Yen-Ling; Chen, Yu-Chie

    2016-10-28

    Surface-assisted laser desorption/ionization (SALDI) coupled with mass spectrometry (MS) is frequently used to analyse small organics owing to its clean background. Inorganic materials can be used as energy absorbers and the transfer medium to facilitate the desorption/ionization of analytes; thus, they are used as SALDI-assisting materials. Many studies have demonstrated the usefulness of SALDI-MS in quantitative analysis of small organics. However, some characteristics occurring in SALDI-MS require certain attention to ensure the reliability of the quantitative analysis results. The appearance of a coffee-ring effect in SALDI sample preparation is the primary factor that can affect quantitative SALDI-MS analysis results. However, to the best of our knowledge, there are no reports relating to quantitative SALDI-MS analysis that discuss or consider this effect. In this study, the coffee-ring effect is discussed using nanoparticles and nanostructured substrates as SALDI-assisting materials to show how this effect influences SALDI-MS analysis results. Potential solutions for overcoming the existing problems are also suggested.This article is part of the themed issue 'Quantitative mass spectrometry'. PMID:27644973

  10. Multivariate analysis of progressive thermal desorption coupled gas chromatography-mass spectrometry.

    SciTech Connect

    Van Benthem, Mark Hilary; Mowry, Curtis Dale; Kotula, Paul Gabriel; Borek, Theodore Thaddeus, III

    2010-09-01

    Thermal decomposition of poly dimethyl siloxane compounds, Sylgard{reg_sign} 184 and 186, were examined using thermal desorption coupled gas chromatography-mass spectrometry (TD/GC-MS) and multivariate analysis. This work describes a method of producing multiway data using a stepped thermal desorption. The technique involves sequentially heating a sample of the material of interest with subsequent analysis in a commercial GC/MS system. The decomposition chromatograms were analyzed using multivariate analysis tools including principal component analysis (PCA), factor rotation employing the varimax criterion, and multivariate curve resolution. The results of the analysis show seven components related to offgassing of various fractions of siloxanes that vary as a function of temperature. Thermal desorption coupled with gas chromatography-mass spectrometry (TD/GC-MS) is a powerful analytical technique for analyzing chemical mixtures. It has great potential in numerous analytic areas including materials analysis, sports medicine, in the detection of designer drugs; and biological research for metabolomics. Data analysis is complicated, far from automated and can result in high false positive or false negative rates. We have demonstrated a step-wise TD/GC-MS technique that removes more volatile compounds from a sample before extracting the less volatile compounds. This creates an additional dimension of separation before the GC column, while simultaneously generating three-way data. Sandia's proven multivariate analysis methods, when applied to these data, have several advantages over current commercial options. It also has demonstrated potential for success in finding and enabling identification of trace compounds. Several challenges remain, however, including understanding the sources of noise in the data, outlier detection, improving the data pretreatment and analysis methods, developing a software tool for ease of use by the chemist, and demonstrating our belief that

  11. Statistical discrimination of black gel pen inks analysed by laser desorption/ionization mass spectrometry.

    PubMed

    Weyermann, Céline; Bucher, Lukas; Majcherczyk, Paul; Mazzella, Williams; Roux, Claude; Esseiva, Pierre

    2012-04-10

    Pearson correlation coefficients were applied for the objective comparison of 30 black gel pen inks analysed by laser desorption ionization mass spectrometry (LDI-MS). The mass spectra were obtained for ink lines directly on paper using positive and negative ion modes at several laser intensities. This methodology has the advantage of taking into account the reproducibility of the results as well as the variability between spectra of different pens. A differentiation threshold could thus be selected in order to avoid the risk of false differentiation. Combining results from positive and negative mode yielded a discriminating power up to 85%, which was better than the one obtained previously with other optical comparison methodologies. The technique also allowed discriminating between pens from the same brand. PMID:22115723

  12. Rapid determination of drugs and semivolatile organics by direct thermal desorption ion trap mass spectrometry

    SciTech Connect

    Wise, M.B.; Ilgner, R.H.; Buchanan, M.V.; Guerin, M.R.

    1991-01-01

    Direct thermal desorption of analytes into an ion trap mass spectrometer (ITMS) is being investigated as a technique for the rapid screening of a wide variety of samples for target semivolatile organic compounds. This includes the direct detection of drugs in physiological fluids, semivolatile organic pollutants in water and waste samples, and air pollutants collected on sorbent cartridges. In order to minimize the analysis time, chromatographic separation is not performed on the sample prior to introduction into the ITMS. Instead, selective chemical ionization and tandem mass spectrometry (MS/MS) are used achieve the specificity required for the target analytes. Detection limits are typically 10--50 ppb using a 1 uL aliquot of a liquid sample without preconcentration. Sample turn-around time is 2 to 5 minutes and 3 to 5 target analytes can be quantitatively determined simultaneously. 6 figs.

  13. Ammonium Ion Exchanged Zeolite for Laser Desorption/Ionization Mass Spectrometry of Phosphorylated Peptides

    PubMed Central

    Yang, Mengrui; Fujino, Tatsuya

    2015-01-01

    α-Cyano-4-hydroxycinnamic acid (CHCA), an organic matrix molecule for matrix-assisted laser desorption/ionization mass spectrometry, was adsorbed to NH4+-type zeolite surface, and this new matrix was used for the detection of low-molecular-weight compounds. It was found that this matrix could simplify the mass spectrum in the low-molecular-weight region and prevent interference from fragments and alkali metal ion adducted species. CHCA adsorbed to NH4+-type ZSM5 zeolite (CHCA/NH4ZSM5) was used to measure atropine and aconitine, two toxic alkaloids in plants. In addition, CHCA/NH4ZSM5 enabled us to detect phosphorylated peptides; peaks of the protonated peptides had higher intensities than the peaks observed using CHCA only. PMID:26448749

  14. Matrix-Assisted Laser Desorption Ionization Imaging Mass Spectrometry: In Situ Molecular Mapping

    PubMed Central

    Angel, Peggi M.; Caprioli, Richard M.

    2013-01-01

    Matrix-assisted laser desorption ionization imaging mass spectrometry (IMS) is a relatively new imaging modality that allows mapping of a wide range of biomolecules within a thin tissue section. The technology uses a laser beam to directly desorb and ionize molecules from discrete locations on the tissue that are subsequently recorded in a mass spectrometer. IMS is distinguished by the ability to directly measure molecules in situ ranging from small metabolites to proteins, reporting hundreds to thousands of expression patterns from a single imaging experiment. This article reviews recent advances in IMS technology, applications, and experimental strategies that allow it to significantly aid in the discovery and understanding of molecular processes in biological and clinical samples. PMID:23259809

  15. Atomic Force Microscope Controlled Topographical Imaging and Proximal Probe Thermal Desorption/Ionization Mass Spectrometry Imaging

    SciTech Connect

    Ovchinnikova, Olga S; Kjoller, Kevin; Hurst, Gregory {Greg} B; Pelletier, Dale A; Van Berkel, Gary J

    2014-01-01

    This paper reports on the development of a hybrid atmospheric pressure atomic force microscopy/mass spectrometry imaging system utilizing nano-thermal analysis probes for thermal desorption surface sampling with subsequent atmospheric pressure chemical ionization and mass analysis. The basic instrumental setup and the general operation of the system were discussed and optimized performance metrics were presented. The ability to correlate topographic images of a surface with atomic force microscopy and a mass spectral chemical image of the same surface, utilizing the same probe without moving the sample from the system, was demonstrated. Co-registered mass spectral chemical images and atomic force microscopy topographical images were obtained from inked patterns on paper as well as from a living bacterial colony on an agar gel. Spatial resolution of the topography images based on pixel size (0.2 m x 0.8 m) was better than the resolution of the mass spectral images (2.5 m x 2.0 m), which were limited by current mass spectral data acquisition rate and system detection levels.

  16. High-resolution field desorption/ionization fourier transform ion cyclotron resonance mass analysis of nonpolar molecules.

    PubMed

    Schaub, Tanner M; Hendrickson, Christopher L; Qian, Kuangnan; Quinn, John P; Marshall, Alan G

    2003-05-01

    We report the first field desorption ionization broadband high-resolution (m/Deltam(50%) approximately 65 000) mass spectra. We have interfaced a field ionization/field desorption source to a home-built 9.4-T FT-ICR mass spectrometer. The instrumental configuration employs convenient sample introduction (in-source liquid injection) and external ion accumulation. We demonstrate the utility of this configuration by generating high-resolution positive-ion mass spectra of C(60) and a midboiling crude oil distillate. The latter contains species not accessible by common soft-ionization methods, for example, low-voltage electron ionization, electrospray ionization, and matrix-assisted laser desorption/ionization. The present work demonstrates significant advantages of FI/FD FT-ICR MS for analysis of nonpolar molecules in complex mixtures.

  17. Cobalt coated substrate for matrix-free analysis of small molecules by laser desorption/ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Yalcin, Talat; Li, Liang

    2009-12-01

    Small molecule analysis is one of the most challenging issues in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. We have developed a cobalt coated substrate as a target for matrix-free analysis of small molecules in laser desorption/ionization mass spectrometry. Cobalt coating of 60-70 nm thickness has been characterized by scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, and laser induced breakdown spectroscopy. This target facilitates hundreds of samples to be spotted and analyzed without mixing any matrices, in a very short time. This can save a lot of time and money and can be a very practical approach for the analysis of small molecules by laser desorption/ionization mass spectrometry.

  18. Studies of metallofullerene primary soots by laser and thermal desorption mass spectrometry

    SciTech Connect

    Moro, L.; Ruoff, R.S.; Becker, C.H.; Lorents, D.C.; Malhotra, R. )

    1993-07-01

    Laser desorption (LD) and thermal desorption (TD) mass spectra of the metallofullerenes found in arc-produced primary soots have been studied for a large variety of alkaline earth and lanthanide elements. The metallofullerene ratios found in the LD spectra indicate that two distinct groups are observed: Sc, Y, La, Ce, Pr, Nd, Gd, Tb, Ho, Er, and Lu (group A) and Ca, Sr, Sm, Eu, and Yb (group B). The TD spectra of most of these same soots also separate into two groups that contain the same elements as groups A and B. Group A metallofullerenes show strong signals in both LD and TD spectra. Group B metallofullerenes are distinguished by their presence in the LD spectra but absence in the TD spectra. From the general ionic behavior of the elements of these groups, and recent studies of the endohedral oxidation states, we propose that the oxidation states are +3 for group A and +2 for group B. C[sub 70] metallofullerenes are anomalous in that they are absent in TD spectra for all group A and B elements, even at T = 750[degrees]C, but present in LD spectra. 31 refs., 4 figs., 2 tabs.

  19. Characterization of ballpoint pen inks by thermal and desorption and gas chromatography-mass spectrometry.

    PubMed

    Bügler, Jürgen H; Buchner, Hans; Dallmayer, Anton

    2005-09-01

    The characterization of ink on paper is of importance for dating and comparing questioned ink entries in forensic document examination. Inks are commonly characterized by their colorant profile that is identified by well-established analytical methods. Numerous ink formulations show identical colorant profiles, though. In order to differentiate inks that are not distinguishable by colorant analysis, a method for the characterization of colorless ink ingredients, namely binders, solvents and additives is necessary. In this paper, we propose a technique for the analysis of colorless compounds in ballpoint inks using direct thermal desorption of the ink on paper followed by chemical analysis of the desorbed volatile compounds by gas chromatography-mass spectrometry. As compared to liquid extraction and subsequent analysis of the extracts, the technique avoids possible contamination risks. Sensitivity is very high due to the enrichment of volatile components by thermal desorption. Even from old samples, the chromatograms obtained by the method enable the determination of binder polymers, solvents and additives. Pure binders as used by ink manufacturers were analyzed for unambiguous assignment of analytical results to specific polymers. To prove the practical applicability, we analyzed 121 ballpoint pens, not all having the same colorant profile, and grouped the pens into resin and solvent categories. PMID:16225233

  20. Detection of Biosignatures by Geomatrix-Assisted Laser Desorption/Ionization (GALDI) Mass Spectrometry

    SciTech Connect

    Jill R. Scott; Beizhan Yan; Daphne L. Stoner; J. Michelle Kotler; Nancy W. Hinman

    2007-04-01

    Identification of mineral-associated biosignatures is of significance for retrieving biochemical information from geological records here on Earth and detecting signs of life on other planets, such as Mars. The importance of the geomatrix for identifying amino acids (e.g., histidine, threonine, and cysteine) and small proteins (e.g., gramicidin S) was investigated by laser desorption Fourier transform mass spectrometry. The investigated geomatrices include analogues of Fe-bearing minerals such as hematite and Na-bearing evaporites (e.g., halite). Samples were prepared by two methods: 1) application of analyte to the geomatrix surface and 2) production of homogenous analyte:geomatrix mixtures. Comparison of the two sample preparation methods revealed that the mixing method produces a better signal/noise ratio than surface application for the analyses of amino acids. The composition of the geomatrix has a profound influence on the detection of biomolecules. Peaks corresponding to the cation-attached biomolecular ions were observed for the Na-bearing evaporite analogue. No detectable peaks for the biomolecular ion species were observed when the biomolecules were associated with Fe-bearing minerals. Instead, only minor peaks were observed that may correspond to ions from fragments of the biomolecules. Depending on the underlying mineral composition, geomatrix-assisted laser desorption/ionization shows promise for directly identifying biosignatures associated with minerals.

  1. Electroless plating of silver nanoparticles on porous silicon for laser desorption/ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Yan, Hong; Xu, Ning; Huang, Wen-Yi; Han, Huan-Mei; Xiao, Shou-Jun

    2009-03-01

    An improved DIOS (desorption ionization on porous silicon) method for laser desorption/ionization mass spectrometry (LDI MS) by electroless plating of silver nanoparticles (AgNPs) on porous silicon (PSi) was developed. By addition of 4-aminothiophenol (4-ATP) into the AgNO3 plating solution, the plating speed can be slowed down and simultaneously 4-ATP self-assembled monolayers (SAMs) on AgNPs (4-ATP/AgNPs) were formed. Both AgNPs and 4-ATP/AgNPs coated PSi substrates present much higher stability, sensitivity and reproducibility for LDI MS than the un-treated porous silicon ones. Their shelf life in air was tested for several weeks to a month and their mass spectra still displayed the same high quality and sensitivity as the freshly prepared ones. And more 4-ATP SAMs partly play a role of matrix to increase the ionization efficiency. A small organic molecule of tetrapyridinporphyrin (TPyP), oligomers of polyethylene glycol (PEG 400 and 2300), and a peptide of oxytocin were used as examples to demonstrate the feasibility of the silver-plated PSi as a matrix-free-like method for LDI MS. This approach can obtain limits of detection to femtomoles for TPyP, subpicomoles for oxytocin, and picomoles for PEG 400 and 2300, comparable to the traditional matrix method and much better than the DIOS method. It simplifies the sample preparation as a matrix-free-like method without addition of matrix molecules and homogenizes the sample spread over the spot for better and more even mass signals.

  2. Isomeric differentiation of polycyclic aromatic hydrocarbons using silver nitrate reactive desorption electrospray ionization mass spectrometry

    PubMed Central

    Eftekhari, Mohammad; Ismail, Ali I.; Zare, Richard N.

    2014-01-01

    RATIONALE Polycyclic aromatic hydrocarbons (PAHs) are nonpolar and difficult to detect by desorption electrospray ionization. We present a new detection method based on cationization with silver ions, which has the added advantage of being able to differentiate PAHs with the same mass but different structure. METHODS 9,10-Diphenylanthracene and triptycene, in addition to four different groups of PAH isomers: (1) anthracene and phenanthrene, (2) pyrene and fluoranthene, (3) benz[a]anthracene, benz[b]anthracene (tetracene), and chrysene (4) benzo[a]pyrene and benzo[k]fluoranthene, were deposited on a paper surface and bombarded with methanol droplets containing silver nitrate. The resulting microdroplets entered a quadruple mass spectrometer for mass analysis. RESULTS The mass spectrum shows [PAH]+, [Ag + OH + PAH]+, and [Ag(PAH)n]+ n (n = 1, 2) (and [PAH + O2]+ in the case of benz[b]anthracene) ions. PAHs having a bay structure, such as phenanthrene, showed a different tendency to interact with silver ions from those PAHs having a linear arrangement of the fused benzene rings, such as anthracene. The ratios of the [PAH]+ peak intensity to that of [Ag–PAH]+, [Ag + OH + PAH]+, [Ag(PAH)2]+, and [PAH + O2]+ were used to differentiate the PAH isomers sharing the same molecular formula with different structures. For isomeric mixtures the [PAH]+ to [Ag + OH + PAH]+ ratio was found to be the most useful parameter. The uncertainty in the mole fraction of an isomeric mixture was ±0.09, 0.13, ±0.25, and ±0.1 for phenanthrene-anthracene, fl benz[a] anthracene-chrysene, and benzo[a]pyrene-benzo[k]fluoranthene, respectively. CONCLUSIONS A simple method has been developed for the detection of PAHs in desorption electrospray ionization mass spectrometry based on Ag(I) cationization. The method showed a capability to differentiate PAHs isomers (having the same molecular mass) in isomeric mixture with an uncertainty in the mole fraction of about 0.1. At high inlet temperature

  3. Analysis of mainstream and sidestream cigarette smoke particulate matter by laser desorption mass spectrometry.

    PubMed

    Schramm, Sébastien; Carré, Vincent; Scheffler, Jean-Luc; Aubriet, Frédéric

    2011-01-01

    Laser desorption ionization Fourier transform ion cyclotron resonance mass spectrometry (LDI-FTICRMS) was used to investigate particulate matter (PM) associated with mainstream (MSS) and sidestream cigarette smokes (SSS). The high mass resolution and the high mass measurement accuracy allowed a molecular formula for each detected signal in the 150-500 m/z range to be assigned. The high number of peaks observed in mass spectra required additional data processing to extract information. In this context, Kendrick maps and Van Krevelen diagrams were drawn. These postacquisition treatments were used to more easily compare different cigarette smokes: (i) MSS from different cigarettes and (ii) MSS and SSS from the same cigarette. In both ion detection modes, most of the detected species were found to be attributed to C(6-31)H(2-35)N(0-7)O(0-9) compounds. The compounds observed in the study of SSS appeared to be more unsaturated and less oxygenated than those observed when MSS of the same cigarette was investigated.

  4. 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

    SciTech Connect

    Perdian, David C.

    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.

  5. Review of Matrix-Assisted Laser Desorption Ionization-Imaging Mass Spectrometry for Lipid Biochemical Histopathology

    PubMed Central

    Yalcin, Emine B.

    2015-01-01

    Matrix-Assisted Laser Desorption Ionization-Imaging Mass Spectrometry (MALDI-IMS) is a rapidly evolving method used for the in situ visualization and localization of molecules such as drugs, lipids, peptides, and proteins in tissue sections. Therefore, molecules such as lipids, for which antibodies and other convenient detection reagents do not exist, can be detected, quantified, and correlated with histopathology and disease mechanisms. Furthermore, MALDI-IMS has the potential to enhance our understanding of disease pathogenesis through the use of “biochemical histopathology”. Herein, we review the underlying concepts, basic methods, and practical applications of MALDI-IMS, including post-processing steps such as data analysis and identification of molecules. The potential utility of MALDI-IMS as a companion diagnostic aid for lipid-related pathological states is discussed. PMID:26209083

  6. Reconstruction and feature selection for desorption electrospray ionization mass spectroscopy imagery

    NASA Astrophysics Data System (ADS)

    Gao, Yi; Zhu, Liangjia; Norton, Isaiah; Agar, Nathalie Y. R.; Tannenbaum, Allen

    2014-03-01

    Desorption electrospray ionization mass spectrometry (DESI-MS) provides a highly sensitive imaging technique for differentiating normal and cancerous tissue at the molecular level. This can be very useful, especially under intra-operative conditions where the surgeon has to make crucial decision about the tumor boundary. In such situations, the time it takes for imaging and data analysis becomes a critical factor. Therefore, in this work we utilize compressive sensing to perform the sparse sampling of the tissue, which halves the scanning time. Furthermore, sparse feature selection is performed, which not only reduces the dimension of data from about 104 to less than 50, and thus significantly shortens the analysis time. This procedure also identifies biochemically important molecules for further pathological analysis. The methods are validated on brain and breast tumor data sets.

  7. Direct Surface Analysis of Fungal Species by Matrix-assisted Laser Desorption/Ionization Mass Spectrometry

    SciTech Connect

    Valentine, Nancy B. ); Wahl, Jon H. ); Kingsley, Mark T. ); Wahl, Karen L. )

    2001-12-01

    Intact spores and/or hyphae of Aspergillus niger, Rhizopus oryzae, Trichoderma reesei and Phanerochaete chrysosporium are analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). This study investigates various methods of sample preparation and matrices to determine optimum collection and analysis criteria for fungal analysis by MALDI-MS. Fungi are applied to the MALDI sample target as untreated, sonicated, acid/heat treated, or blotted directly from the fungal culture with double-stick tape. Ferulic acid or sinapinic acid matrix solution is layered over the dried samples and analyzed by MALDI-MS. Statistical analysis of the data show that simply using double stick tape to collect and transfer to a MALDI sample plate typically worked as well as the other preparation methods, but requires the least sample handling.

  8. Beer fingerprinting by Matrix-Assisted Laser Desorption-Ionisation-Time of Flight Mass Spectrometry.

    PubMed

    Šedo, Ondrej; Márová, Ivana; Zdráhal, Zbyněk

    2012-11-15

    A method allowing parallel fingerprinting of proteins and maltooligosaccharides directly from untreated beer samples is presented. These two classes of compounds were detected by Matrix-Assisted Laser Desorption-Ionisation-Time of Flight-Mass Spectrometry (MALDI-TOF-MS) analysis of beer mixed with 2,5-dihydroxybenzoic acid solution. The maltooligosaccharide profiles acquired from the MALDI sample spot center were not found characteristic for beers of different source and technology. On the other hand, according to profiles containing protein signals acquired from crystals formed on the border of the MALDI sample spot, we were able to distinguish beer samples of the same brand produced by different breweries. The discriminatory abilities of the method were further examined on a set of 17 lager beers, where the fingerprints containing protein signals enabled resolution of majority of examined brands. We propose MALDI-TOF-MS profiling as a rapid tool for beer brewing technology process monitoring, quality control, and determination of beer authenticity.

  9. Miniaturizing sample spots for matrix-assisted laser desorption/ionization mass spectrometry

    PubMed Central

    Tu, Tingting; Gross, Michael L.

    2009-01-01

    The trend of miniaturization in bioanalytical chemistry is shifting from technical development to practical application. In matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), progress in miniaturizing sample spots has been driven by the needs to increase sensitivity and speed, to interface with other analytical microtechnologies, and to develop miniaturized instrumentation. We review recent developments in miniaturizing sample spots for MALDI-MS. We cover both target modification and microdispensing technologies, and we emphasize the benefits with respect to sensitivity, throughput and automation. We hope that this review will encourage further method development and application of miniaturized sample spots for MALDI-MS, so as to expand applications in analytical chemistry, protein science and molecular biology. PMID:20161086

  10. Shotgun Approach for Quantitative Imaging of Phospholipids Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Lanekoff, Ingela T.; Thomas, Mathew; Laskin, Julia

    2014-02-04

    Mass spectrometry imaging (MSI) has been extensively used for determining spatial distributions of molecules in biological samples, and there is increasing interest in using MSI for quantification. Nanospray desorption electrospray ionization, or nano-DESI, is an ambient MSI technique where a solvent is used for localized extraction of molecules followed by nanoelectrospray ionization. Doping the nano-DESI solvent with carefully selected standards enables online quantification during MSI experiments. In this proof-of-principle study, we demonstrate this quantification approach can be extended to provide shotgun-like quantification of phospholipids in thin brain tissue sections. Specifically, two phosphatidylcholine (PC) standards were added to the nano-DESI solvent for simultaneous imaging and quantification of 22 PC species observed in nano-DESI MSI. Furthermore, by combining the quantitative data obtained in the individual pixels, we demonstrate quantification of these PC species in seven different regions of a rat brain tissue section.

  11. Development and Applications of Liquid Sample Desorption Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zheng, Qiuling; Chen, Hao

    2016-06-01

    Desorption electrospray ionization mass spectrometry (DESI-MS) is a recent advance in the field of analytical chemistry. This review surveys the development of liquid sample DESI-MS (LS-DESI-MS), a variant form of DESI-MS that focuses on fast analysis of liquid samples, and its novel analy-tical applications in bioanalysis, proteomics, and reaction kinetics. Due to the capability of directly ionizing liquid samples, liquid sample DESI (LS-DESI) has been successfully used to couple MS with various analytical techniques, such as microfluidics, microextraction, electrochemistry, and chromatography. This review also covers these hyphenated techniques. In addition, several closely related ionization methods, including transmission mode DESI, thermally assisted DESI, and continuous flow-extractive DESI, are briefly discussed. The capabilities of LS-DESI extend and/or complement the utilities of traditional DESI and electrospray ionization and will find extensive and valuable analytical application in the future.

  12. Identification of Bacillus Spores by Matrix-Assisted Laser Desorption Ionization–Mass Spectrometry

    PubMed Central

    Hathout, Yetrib; Demirev, Plamen A.; Ho, Yen-Peng; Bundy, Jonathan L.; Ryzhov, Victor; Sapp, Lisa; Stutler, James; Jackman, Joany; Fenselau, Catherine

    1999-01-01

    Unique patterns of biomarkers were reproducibly characterized by matrix-assisted laser desorption ionization (MALDI)–mass spectrometry and were used to distinguish Bacillus species members from one another. Discrimination at the strain level was demonstrated for Bacillus cereus spores. Lipophilic biomarkers were invariant in Bacillus globigii spores produced in three different media and in B. globigii spores stored for more than 30 years. The sensitivity was less than 5,000 cells deposited for analysis. Protein biomarkers were also characterized by MALDI analysis by using spores treated briefly with corona plasma discharge. Protein biomarkers were readily desorbed following this treatment. The effect of corona plasma discharge on the spores was examined. PMID:10508053

  13. Quantum dots assisted laser desorption/ionization mass spectrometric detection of carbohydrates: qualitative and quantitative analysis.

    PubMed

    Bibi, Aisha; Ju, Huangxian

    2016-04-01

    A quantum dots (QDs) assisted laser desorption/ionization mass spectrometric (QDA-LDI-MS) strategy was proposed for qualitative and quantitative analysis of a series of carbohydrates. The adsorption of carbohydrates on the modified surface of different QDs as the matrices depended mainly on the formation of hydrogen bonding, which led to higher MS intensity than those with conventional organic matrix. The effects of QDs concentration and sample preparation method were explored for improving the selective ionization process and the detection sensitivity. The proposed approach offered a new dimension to the application of QDs as matrices for MALDI-MS research of carbohydrates. It could be used for quantitative measurement of glucose concentration in human serum with good performance. The QDs served as a matrix showed the advantages of low background, higher sensitivity, convenient sample preparation and excellent stability under vacuum. The QDs assisted LDI-MS approach has promising application to the analysis of carbohydrates in complex biological samples.

  14. Molecular Characterization of Organic Aerosols Using Nanospray Desorption/Electrospray Ionization-Mass Spectrometry

    SciTech Connect

    Roach, Patrick J.; Laskin, Julia; Laskin, Alexander

    2010-10-01

    Nanospray desorption electrospray ionization (Nano-DESI) combined with high-resolution mass spectrometry (HR/MS) is a promising approach for detailed chemical characterization of atmospheric organic aerosol (OA) collected in laboratory and field experiments. In Nano-DESI analyte is desorbed into a solvent bridge formed between two capillaries and the analysis surface, which enables fast and efficient characterization of OA collected on substrates without special sample preparation. Stable signals achieved using Nano-DESI make it possible to obtain high-quality HR/MS data using only a small amount of material (<10 ng). Furthermore, Nano-DESI enables efficient detection of chemically labile compounds in OA, which is important for understanding chemical aging phenomena.

  15. Applications of electrospray laser desorption ionization mass spectrometry for document examination.

    PubMed

    Cheng, Sy-Chyi; Lin, Yu-Shan; Huang, Ming-Zong; Shiea, Jentaie

    2010-01-01

    We have employed electrospray laser desorption ionization mass spectrometry (ELDI-MS) to rapidly characterize certain classes of compounds--the inks within the characters made by inks and inkjet printer on regular paper and the chemical compounds within thermal papers. This ELDI-MS approach allowed the ink and paper samples to be distinguished in terms of their chemical compositions. Sample pretreatment was unnecessary and the documents were practically undamaged after examination. The ink chemicals on the documents were desorbed through laser irradiation (sampling spot area: <100 microm(2)); the desorbed molecules then entered an electrospray plume--prepared from an acidic methanol/water solution (50%)--where they became ionized through fusion or ion-molecule reactions with the charged solvent species and droplets in the plume.

  16. Investigation of Cell Surfaces using Microplasma-Assisted Desorption/Ionization Mass Spectroscopy

    NASA Astrophysics Data System (ADS)

    Symonds, Joshua; Sun, Lan; Fernández, Facundo; Orlando, Thomas

    2008-10-01

    Low-temperature, atmospheric pressure microplasmas have been developed for a wide array of uses. We have investigated one type of these devices, a Microhollow Cathode Discharge (MHCD) for desorbing and ionizing samples to be analyzed with standard mass spectroscopy techniques. Our work includes the development and use of MHCD's to analyze solid and liquid phase samples, with particular attention given to biologically-relevant substances. The goal of this line of research is to investigate, without causing undue fragmentation, the compounds present on and within cell membranes. By varying the properties of the plasma, including electron temperature, plasma density, and the plasma's interactions with the sample, we seek to investigate the role of different plasma components in the desorption/ionization events. Specifically, we seek to determine whether the process is dominated by emitted electrons, high energy (VUV) photons, metastable particles, or a combination thereof.

  17. Non-traditional applications of laser desorption/ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    McAlpin, Casey R.

    Seven studies were carried out using laser desorption/ionization mass spectrometry (LDI MS) to develop enhanced methodologies for a variety of analyte systems by investigating analyte chemistries, ionization processes, and elimination of spectral interferences. Applications of LDI and matrix assisted laser/desorption/ionization (MALDI) have been previously limited by poorly understood ionization phenomena, and spectral interferences from matrices. Matrix assisted laser desorption ionization MS is well suited to the analysis of proteins. However, the proteins associated with bacteriophages often form complexes which are too massive for detection with a standard MALDI mass spectrometer. As such, methodologies for pretreatment of these samples are discussed in detail in the first chapter. Pretreatment of bacteriophage samples with reducing agents disrupted disulfide linkages and allowed enhanced detection of bacteriophage proteins. The second chapter focuses on the use of MALDI MS for lipid compounds whose molecular mass is significantly less than the proteins for which MALDI is most often applied. The use of MALDI MS for lipid analysis presented unique challenges such as matrix interference and differential ionization efficiencies. It was observed that optimization of the matrix system, and addition of cationization reagents mitigated these challenges and resulted in an enhanced methodology for MALDI MS of lipids. One of the challenges commonly encountered in efforts to expand MALDI MS applications is as previously mentioned interferences introduced by organic matrix molecules. The third chapter focuses on the development of a novel inorganic matrix replacement system called metal oxide laser ionization mass spectrometry (MOLI MS). In contrast to other matrix replacements, considerable effort was devoted to elucidating the ionization mechanism. It was shown that chemisorption of analytes to the metal oxide surface produced acidic adsorbed species which then

  18. Laser desorption time-of-flight mass spectrometry of ultraviolet photo-processed ices

    SciTech Connect

    Paardekooper, D. M. Bossa, J.-B.; Isokoski, K.; Linnartz, H.

    2014-10-01

    A new ultra-high vacuum experiment is described that allows studying photo-induced chemical processes in interstellar ice analogues. MATRI²CES - a Mass Analytical Tool to study Reactions in Interstellar ICES applies a new concept by combining laser desorption and time-of-flight mass spectrometry with the ultimate goal to characterize in situ and in real time the solid state evolution of organic compounds upon UV photolysis for astronomically relevant ice mixtures and temperatures. The performance of the experimental setup is demonstrated by the kinetic analysis of the different photoproducts of pure methane (CH₄) ice at 20 K. A quantitative approach provides formation yields of several new species with up to four carbon atoms. Convincing evidence is found for the formation of even larger species. Typical mass resolutions obtained range from M/ΔM ~320 to ~400 for CH₄ and argon, respectively. Additional tests show that the typical detection limit (in monolayers) is ⩽0.02 ML, substantially more sensitive than the regular techniques used to investigate chemical processes in interstellar ices.

  19. Laser desorption/ionization mass spectrometry of diesel particulate matter with charge-transfer complexes.

    PubMed

    Carré, Vincent; Vernex-Loset, Lionel; Krier, Gabriel; Manuelli, Pascal; Muller, Jean-François

    2004-07-15

    Polycyclic aromatic hydrocarbons (PAHs) are often associated with complex matrixes such as exhaust diesel particulate matter (DPM), which complicates their study. In that case, laser desorption/ionization mass spectrometry is one of the techniques which ensures their direct analysis in the solid state. We demonstrate in this paper that the use of charge-transfer pi-complexing agents allows us to selectively detect by Fourier transform ion cyclotron resonance mass spectrometry PAHs adsorbed on diesel particles with high sensitivity. 2,4,7-trinitro-9-fluorenone and 7,7',8,8'-tetracyanoquinodimethane pi-acceptor compounds form charge-transfer complexes with PAHs and prevent their evaporation in the mass spectrometer during analysis. Moreover, the production of PAH molecular ions is dramatically increased by laser irradiation of these complexes at short wavelength (221.7 nm) and low power density (5 x 10(6) W cm(-)(2)). This methodology is applied for the first time to the examination of DPM collected during the new European driving cycle for light-duty vehicles. Differentiation criteria may coherently be assigned to engine operating mode (engine temperature, driving conditions). DPM samples can also be easily distinguished in negative ions according to the high sensitivity of this detection mode to sulfate compounds.

  20. New strategies for characterizing ancient proteins using matrix-assisted laser desorption ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Ostrom, Peggy H.; Schall, Michael; Gandhi, Hasand; Shen, Tun-Li; Hauschka, Peter V.; Strahler, John R.; Gage, Douglas A.

    2000-03-01

    Structural characterization of ancient proteins is confounded by the small quantity of material remaining in fossils, difficulties in purification, and the inability to obtain sequence information by classical Edman degradation. We present a microbore reversed phase high performance liquid chromatography (rpHPLC) method for partial purification of small quantities (picomoles) of the bone protein osteocalcin (OC) and subsequent characterization of this material by matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS). The presence of OC in the modern and ancient samples was suggested by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) and radioimmunoassay (RIA). The SDS-PAGE of material isolated from 800 yr BP and 10,000 yr BP bones demonstrates a band consistent with the molecular weight of OC and the RIA indicated OC in concentrations of 0.2 to 450ng/mg of bone for samples between 800 and 53,000 yr BP. In modern samples, we demonstrate the use of MALDI-MS to confirm the molecular weight of intact OC and to sequence OC via peptide mass mapping and a novel derivatization approach with post-source decay analysis. MALDI-MS data for three ancient samples with RIA-confirmed osteocalcin (800 yr BP, 10,000 yr BP and 53,000 yr BP) indicate peaks with a molecular mass within the range of modern OC.

  1. High-Resolution Desorption Electrospray Ionization Mass Spectrometry for Chemical Characterization of Organic Aerosols

    SciTech Connect

    Laskin, Julia; Laskin, Alexander; Roach, Patrick J.; Slysz, Gordon W.; Anderson, Gordon A.; Nizkorodov, Serguei; Bones, David L.; Nguyen, Lucas

    2010-03-01

    Characterization of the chemical composition and chemical transformations of secondary organic aerosol (SOA) is both a major challenge and the area of greatest uncertainty in current aerosol research. This study presents the first application of desorption electrospray ionization combined with high-resolution mass spectrometry (DESI-MS) for detailed chemical characterization and studies of chemical aging of OA collected on Teflon substrates. DESI-MS offers unique advantages both for detailed characterization of chemically labile components in OA that cannot be detected using more traditional electrospray ionization mass spectrometry (ESI-MS) and for studying chemical aging of OA. DESI-MS enables rapid characterization of OA samples collected on substrates by eliminating the sample preparation stage. In addition, it enables detection and structural characterization of chemically labile molecules in OA samples by minimizing the residence time of analyte in the solvent. SOA produced by the ozonolysis of limonene (LSOA) was allowed to react with gaseous ammonia. Chemical aging resulted in measurable changes in the optical properties of LSOA observed using UV- visible spectroscopy. DESI-MS combined with tandem mass spectrometry experiments (MS/MS) enabled identification of species in aged LSOA responsible for absorption of the visible light. Detailed analysis of the experimental data allowed us to identify chemical changes induced by reactions of LSOA constituents with ammonia and distinguish between different mechanisms of chemical aging.

  2. Identification of Fatty Acids, Phospholipids, and Their Oxidation Products Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry and Electrospray Ionization Mass Spectrometry

    ERIC Educational Resources Information Center

    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…

  3. Transmission geometry laser desorption atmospheric pressure photochemical ionization mass spectrometry for analysis of complex organic mixtures.

    PubMed

    Nyadong, Leonard; Mapolelo, Mmilili M; Hendrickson, Christopher L; Rodgers, Ryan P; Marshall, Alan G

    2014-11-18

    We present laser desorption atmospheric pressure photochemical ionization mass spectrometry (LD/APPCI MS) for rapid throughput analysis of complex organic mixtures, without the need for matrix, electric discharge, secondary electrospray, or solvents/vaporizers. Analytes dried on a microscope slide are vaporized in transmission geometry by a laser beam aligned with the atmospheric pressure inlet of the mass spectrometer. The laser beam initiates a cascade of reactions in the region between the glass slide and MS inlet, leading to generation of reagent ions for chemical ionization of vaporized analyte. Positive analyte ions are generated predominantly by proton transfer, charge exchange, and hydride abstraction, whereas negative ions are generated by electron capture or proton transfer reactions, enabling simultaneous analysis of saturated, unsaturated, and heteroatom-containing hydrocarbons. The absence of matrix interference renders LD/APPCI MS particularly useful for analysis of small molecules (<2000 Da) such as those present in petroleum crude oil and petroleum deposits. [M + H](+) and M(+•) dominate the positive-ion mass spectra for olefins and polyaromatic hydrocarbons, whereas saturated hydrocarbons are observed mainly as [M - H](+) and/or M(+•). Heteroatom-containing hydrocarbons are observed predominantly as [M + H](+). [M - H](-) and M(-•) are the dominant negative ions observed for analytes of lower gas-phase basicity or higher electron affinity than O2. The source was coupled with a 9.4 T Fourier transform ion cyclotron resonance mass spectrometer (FTICR MS) to resolve and identify thousands of peaks from Athabasca bitumen heavy vacuum gas oil distillates (400-425 and 500-538 °C), enabling simultaneous characterization of their polar and nonpolar composition. We also applied LD/APPCI FTICR MS for rapid analysis of sodium and calcium naphthenate deposits with little to no sample pretreatment to provide mass spectral fingerprints that enable

  4. Transmission geometry laser desorption atmospheric pressure photochemical ionization mass spectrometry for analysis of complex organic mixtures.

    PubMed

    Nyadong, Leonard; Mapolelo, Mmilili M; Hendrickson, Christopher L; Rodgers, Ryan P; Marshall, Alan G

    2014-11-18

    We present laser desorption atmospheric pressure photochemical ionization mass spectrometry (LD/APPCI MS) for rapid throughput analysis of complex organic mixtures, without the need for matrix, electric discharge, secondary electrospray, or solvents/vaporizers. Analytes dried on a microscope slide are vaporized in transmission geometry by a laser beam aligned with the atmospheric pressure inlet of the mass spectrometer. The laser beam initiates a cascade of reactions in the region between the glass slide and MS inlet, leading to generation of reagent ions for chemical ionization of vaporized analyte. Positive analyte ions are generated predominantly by proton transfer, charge exchange, and hydride abstraction, whereas negative ions are generated by electron capture or proton transfer reactions, enabling simultaneous analysis of saturated, unsaturated, and heteroatom-containing hydrocarbons. The absence of matrix interference renders LD/APPCI MS particularly useful for analysis of small molecules (<2000 Da) such as those present in petroleum crude oil and petroleum deposits. [M + H](+) and M(+•) dominate the positive-ion mass spectra for olefins and polyaromatic hydrocarbons, whereas saturated hydrocarbons are observed mainly as [M - H](+) and/or M(+•). Heteroatom-containing hydrocarbons are observed predominantly as [M + H](+). [M - H](-) and M(-•) are the dominant negative ions observed for analytes of lower gas-phase basicity or higher electron affinity than O2. The source was coupled with a 9.4 T Fourier transform ion cyclotron resonance mass spectrometer (FTICR MS) to resolve and identify thousands of peaks from Athabasca bitumen heavy vacuum gas oil distillates (400-425 and 500-538 °C), enabling simultaneous characterization of their polar and nonpolar composition. We also applied LD/APPCI FTICR MS for rapid analysis of sodium and calcium naphthenate deposits with little to no sample pretreatment to provide mass spectral fingerprints that enable

  5. Flash Desorption/Mass Spectrometry for the Analysis of Less- and Nonvolatile Samples Using a Linearly Driven Heated Metal Filament

    NASA Astrophysics Data System (ADS)

    Usmanov, Dilshadbek T.; Ninomiya, Satoshi; Hiraoka, Kenzo

    2013-11-01

    In this paper, the important issue of the desorption of less- and nonvolatile compounds with minimal sample decomposition in ambient mass spectrometry is approached using ambient flash desorption mass spectrometry. The preheated stainless steel filament was driven down and up along the vertical axis in 0.3 s. At the lowest position, it touched the surface of the sample with an invasion depth of 0.1 mm in 50 ms (flash heating) and was removed from the surface (fast cooling). The heating rate corresponds to ~104 °C/s at the filament temperature of 500 °C. The desorbed gaseous molecules were ionized by using a dielectric barrier discharge ion source, and the produced ions were detected by a time-of-flight (TOF) mass spectrometer. Less-volatile samples, such as pharmaceutical tablets, narcotics, explosives, and C60 gave molecular and protonated molecule ions as major ions with thermal decomposition minimally suppressed. For synthetic polymers (PMMA, PLA, and PS), the mass spectra reflected their backbone structures because of the suppression of the sequential thermal decompositions of the primary products. The present technique appears to be suitable for high-throughput qualitative analyses of many types of solid samples in the range from a few ng to 10 μg with minimal sample consumption. Some contribution from tribodesorption in addition to thermal desorption was suggested for the desorption processes. [Figure not available: see fulltext.

  6. On-probe pyrolysis desorption ecectrospray ionization (DESI) mass spectrometry for the analysis of non-volatile pyrolysis products

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An on-probe pyrolyzer has been constructed and interfaced with desorption electrospray ionization (DESI) mass spectrometry (MS) for the rapid analysis of non-volatile pyrolysis products. The detection and analysis of non-volatile pyrolysis products of peptides, proteins and the synthetic polymer pol...

  7. Atmospheric Pressure-Thermal Desorption (AP-TD)/Electrospray Ionization-Mass Spectrometry for the Rapid Analysis of Bacillus Spores

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A technique is described where an atmospheric pressure-thermal desorption (AP-TD) device and electrospray ionization (ESI)-mass spectrometry are coupled and used for the rapid analysis of Bacillus spores in complex matrices. The resulting AP-TD/ESI-MS technique combines the generation of volatile co...

  8. Development of matrix-assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) for plant metabolite analysis

    SciTech Connect

    Korte, Andrew R

    2014-12-01

    This thesis presents efforts to improve the methodology of matrix-assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) as a method for analysis of metabolites from plant tissue samples. The first chapter consists of a general introduction to the technique of MALDI-MSI, and the sixth and final chapter provides a brief summary and an outlook on future work.

  9. Desorption Electrospray Ionization Mass Spectrometry Reveals Lipid Metabolism of Individual Oocytes and Embryos

    PubMed Central

    González-Serrano, Andrés Felipe; Pirro, Valentina; Ferreira, Christina R.; Oliveri, Paolo; Eberlin, Livia S.; Heinzmann, Julia; Lucas-Hahn, Andrea; Niemann, Heiner; Cooks, Robert Graham

    2013-01-01

    Alteration of maternal lipid metabolism early in development has been shown to trigger obesity, insulin resistance, type 2 diabetes and cardiovascular diseases later in life in humans and animal models. Here, we set out to determine (i) lipid composition dynamics in single oocytes and preimplantation embryos by high mass resolution desorption electrospray ionization mass spectrometry (DESI-MS), using the bovine species as biological model, (ii) the metabolically most relevant lipid compounds by multivariate data analysis and (iii) lipid upstream metabolism by quantitative real-time PCR (qRT-PCR) analysis of several target genes (ACAT1, CPT 1b, FASN, SREBP1 and SCAP). Bovine oocytes and blastocysts were individually analyzed by DESI-MS in both positive and negative ion modes, without lipid extraction and under ambient conditions, and were profiled for free fatty acids (FFA), phospholipids (PL), cholesterol-related molecules, and triacylglycerols (TAG). Principal component analysis (PCA) and linear discriminant analysis (LDA), performed for the first time on DESI-MS fused data, allowed unequivocal discrimination between oocytes and blastocysts based on specific lipid profiles. This analytical approach resulted in broad and detailed lipid annotation of single oocytes and blastocysts. Results of DESI-MS and transcript regulation analysis demonstrate that blastocysts produced in vitro and their in vivo counterparts differed significantly in the homeostasis of cholesterol and FFA metabolism. These results should assist in the production of viable and healthy embryos by elucidating in vivo embryonic lipid metabolism. PMID:24073231

  10. An Automated Platform for High-Resolution Tissue Imaging Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Lanekoff, Ingela T.; Heath, Brandi S.; Liyu, Andrey V.; Thomas, Mathew; Carson, James P.; Laskin, Julia

    2012-10-02

    An automated platform has been developed for acquisition and visualization of mass spectrometry imaging (MSI) data using nanospray desorption electrospray ionization (nano-DESI). The new system enables robust operation of the nano-DESI imaging source over many hours. This is achieved by controlling the distance between the sample and the probe by mounting the sample holder onto an automated XYZ stage and defining the tilt of the sample plane. This approach is useful for imaging of relatively flat samples such as thin tissue sections. Custom software called MSI QuickView was developed for visualization of large data sets generated in imaging experiments. MSI QuickView enables fast visualization of the imaging data during data acquisition and detailed processing after the entire image is acquired. The performance of the system is demonstrated by imaging rat brain tissue sections. High resolution mass analysis combined with MS/MS experiments enabled identification of lipids and metabolites in the tissue section. In addition, high dynamic range and sensitivity of the technique allowed us to generate ion images of low-abundance isobaric lipids. High-spatial resolution image acquired over a small region of the tissue section revealed the spatial distribution of an abundant brain metabolite, creatine, in the white and gray matter that is consistent with the literature data obtained using magnetic resonance spectroscopy.

  11. High throughput volatile fatty acid skin metabolite profiling by thermal desorption secondary electrospray ionisation mass spectrometry.

    PubMed

    Martin, Helen J; Reynolds, James C; Riazanskaia, Svetlana; Thomas, C L Paul

    2014-09-01

    The non-invasive nature of volatile organic compound (VOC) sampling from skin makes this a priority in the development of new screening and diagnostic assays. Evaluation of recent literature highlights the tension between the analytical utility of ambient ionisation approaches for skin profiling and the practicality of undertaking larger campaigns (higher statistical power), or undertaking research in remote locations. This study describes how VOC may be sampled from skin and recovered from a polydimethylsilicone sampling coupon and analysed by thermal desorption (TD) interfaced to secondary electrospray ionisation (SESI) time-of-flight mass spectrometry (MS) for the high throughput screening of volatile fatty acids (VFAs) from human skin. Analysis times were reduced by 79% compared to gas chromatography-mass spectrometry methods (GC-MS) and limits of detection in the range 300 to 900 pg cm(-2) for VFA skin concentrations were obtained. Using body odour as a surrogate model for clinical testing 10 Filipino participants, 5 high and 5 low odour, were sampled in Manilla and the samples returned to the UK and screened by TD-SESI-MS and TD-GC-MS for malodour precursors with greater than >95% agreement between the two analytical techniques. Eight additional VFAs were also identified by both techniques with chains 4 to 15 carbons long being observed. TD-SESI-MS appears to have significant potential for the high throughput targeted screening of volatile biomarkers in human skin.

  12. Rapid Detection of Necrosis in Breast Cancer with Desorption Electrospray Ionization Mass Spectrometry

    PubMed Central

    Tata, Alessandra; Woolman, Michael; Ventura, Manuela; Bernards, Nicholas; Ganguly, Milan; Gribble, Adam; Shrestha, Bindesh; Bluemke, Emma; Ginsberg, Howard J.; Vitkin, Alex; Zheng, Jinzi; Zarrine-Afsar, Arash

    2016-01-01

    Identification of necrosis in tumors is of prognostic value in treatment planning, as necrosis is associated with aggressive forms of cancer and unfavourable outcomes. To facilitate rapid detection of necrosis with Mass Spectrometry (MS), we report the lipid MS profile of necrotic breast cancer with Desorption Electrospray Ionization Mass Spectrometry (DESI-MS) imaging validated with statistical analysis and correlating pathology. This MS profile is characterized by (1) the presence of the ion of m/z 572.48 [Cer(d34:1) + Cl]− which is a ceramide absent from the viable cancer subregions; (2) the absence of the ion of m/z 391.25 which is present in small abundance only in viable cancer subregions; and (3) a slight increase in the relative intensity of known breast cancer biomarker ions of m/z 281.25 [FA(18:1)-H]− and 303.23 [FA(20:4)-H]−. Necrosis is accompanied by alterations in the tissue optical depolarization rate, allowing tissue polarimetry to guide DESI-MS analysis for rapid MS profiling or targeted MS imaging. This workflow, in combination with the MS profile of necrosis, may permit rapid characterization of necrotic tumors from tissue slices. Further, necrosis-specific biomarker ions are detected in seconds with single MS scans of necrotic tumor tissue smears, which further accelerates the identification workflow by avoiding tissue sectioning and slide preparation. PMID:27734938

  13. Study of Electrochemical Reactions Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Liu, Pengyuan; Lanekoff, Ingela T.; Laskin, Julia; Dewald, Howard D.; Chen, Hao

    2012-07-03

    The combination of electrochemistry (EC) and mass spectrometry (MS) is a powerful analytical tool for studying mechanisms of redox reactions, identification of products and intermediates, and online derivatization/recognition of analytes. This work reports a new coupling interface for EC/MS by employing nanospray desorption electrospray ionization (nano-DESI), a recently developed ambient ionization method. We demonstrate online coupling of nano-DESI-MS with a traditional electrochemical flow cell, in which the electrolyzed solution emanating from the cell is ionized by nano-DESI for MS analysis. Furthermore, we show first coupling of nano-DESI-MS with an interdigitated array (IDA) electrode enabling chemical analysis of electrolyzed samples directly from electrode surfaces. Because of its inherent sensitivity, nano-DESI enables chemical analysis of small volumes and concentrations of sample solution. Specifically, good-quality signal of dopamine and its oxidized form, dopamine ortho-quinone, was obtained using 10 μL of 1 μM solution of dopamine on the IDA. Oxidation of dopamine, reduction of benzodiazepines, and electrochemical derivatization of thiol groups were used to demonstrate the performance of the technique. Our results show the potential of nano-DESI as a novel interface for electrochemical mass spectrometry research.

  14. Identification of colorants in pigmented pen inks by laser desorption mass spectrometry.

    PubMed

    Papson, Kaitlin; Stachura, Sylwia; Boralsky, Luke; Allison, John

    2008-01-01

    Pigments are rapidly replacing dyes as colorants in pen and printer inks, due to their superior colors and stability. Unfortunately, tools commonly used in questioned document examination for analyzing pen inks, such as TLC, cannot be used for the analysis of insoluble pigments on paper. Laser desorption mass spectrometry is demonstrated here as a tool for analyzing pigment-based pen inks. A pulsed nitrogen laser can be focused onto a pen stroke from a pigmented ink pen on paper, and positive and negative ions representative of the pigment can be generated for subsequent mass spectrometric analysis. Targeted pens for this work were a set of Uni-ball 207 pigmented ink pens containing blue, light blue, orange, green, violet, red, pink, and black inks. Copper phthalocyanine was identified as the pigment used to make both blue inks. A mixture of halogenated copper phthalocyanines were identified in the green ink. Unexpectedly, the pink ink was found to contain a red pigment, Pigment Red 12, treated with a mixture of water-soluble dyes. Each sample yielded ions representative of the pigments present.

  15. Characterization of the Cathode Electrolyte Interface in Lithium Ion Batteries by Desorption Electrospray Ionization Mass Spectrometry.

    PubMed

    Liu, Yao-Min; G Nicolau, Bruno; Esbenshade, Jennifer L; Gewirth, Andrew A

    2016-07-19

    The solid electrolyte interface (SEI) formed via electrolyte decomposition on the anode of lithium ion batteries is largely responsible for the stable cycling of conventional lithium ion batteries. Similarly, there is a lesser-known analogous layer on the cathode side of a lithium ion battery, termed the cathode electrolyte interface (CEI), whose composition and role are debated. To confirm the existence and composition of the CEI, desorption electrospray ionization mass spectrometry (DESI-MS) is applied to study common lithium ion battery cathodes. We observe CEI formation on the LiMn2O4 cathode material after cycling between 3.5 and 4.5 V vs Li/Li(+) in electrolyte solution containing 1 M LiPF6 or LiClO4 in 1:1 (v/v) ethylene carbonate (EC) and dimethyl carbonate (DMC). Intact poly(ethylene glycol) dimethyl ether is identified as the electrolyte degradation product on the cathode surface by the high mass-resolution Orbitrap mass spectrometer. When EC is paired with ethyl methyl carbonate (EMC), poly(ethylene glycol) dimethyl ether, poly(ethylene glycol) ethyl methyl ether, and poly(ethylene glycol) are found on the surface simultaneously. The presence of ethoxy and methoxy end groups indicates both methoxide and ethoxide are produced and involved in the process of oligomerization. Au surfaces cycled under different electrochemical windows as model systems for Li-ion battery anodes are also examined. Interestingly, the identical oligomeric species to those found in the CEI are found on Au surfaces after running five cycles between 2.0 and 0.1 V vs Li/Li(+) in half-cells. These results show that DESI-MS provides intact molecular information on battery electrodes, enabling deeper understanding of the SEI or CEI composition.

  16. Online Investigation of Aqueous-Phase Electrochemical Reactions by Desorption Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Lu, Mei; Liu, Yong; Helmy, Roy; Martin, Gary E.; Dewald, Howard D.; Chen, Hao

    2015-08-01

    Electrochemistry (EC) combined with mass spectrometry (MS) is a powerful tool for elucidation of electrochemical reaction mechanisms. However, direct online analysis of electrochemical reaction in aqueous phase was rarely explored. This paper presents the online investigation of several electrochemical reactions with biological relevance in the aqueous phase, such as nitrosothiol reduction, carbohydrate oxidation, and carbamazepine oxidation using desorption electrospray ionization mass spectrometry (DESI-MS). It was found that electroreduction of nitrosothiols [e.g., nitrosylated insulin B (13-23)] leads to free thiols by loss of NO, as confirmed by online MS analysis for the first time. The characteristic mass shift of 29 Da and the reduced intensity provide a quick way to identify nitrosylated species. Equally importantly, upon collision-induced dissociation (CID), the reduced peptide ion produces more fragment ions than its nitrosylated precursor ion (presumably the backbone fragmentation cannot compete with the facile NO loss for the precursor ion), thus facilitating peptide sequencing. In the case of saccharide oxidation, it was found that glucose undergoes electro-oxidation to produce gluconic acid at alkaline pH, but not at neutral and acidic pHs. Such a pH-dependent electrochemical behavior was also observed for disaccharides such as maltose and cellobiose. Upon electrochemical oxidation, carbamazepine was found to undergo ring contraction and amide bond cleavage, which parallels the oxidative metabolism observed for this drug in leucocytes. The mechanistic information of these redox reactions revealed by EC/DESI-MS would be of value in nitroso-proteome research and carbohydrate/drug metabolic studies.

  17. Investigation of some biologically relevant redox reactions using electrochemical mass spectrometry interfaced by desorption electrospray ionization.

    PubMed

    Lu, Mei; Wolff, Chloe; Cui, Weidong; Chen, Hao

    2012-04-01

    Recently we have shown that, as a versatile ionization technique, desorption electrospray ionization (DESI) can serve as a useful interface to combine electrochemistry (EC) with mass spectrometry (MS). In this study, the EC/DESI-MS method has been further applied to investigate some aqueous phase redox reactions of biological significance, including the reduction of peptide disulfide bonds and nitroaromatics as well as the oxidation of phenothiazines. It was found that knotted/enclosed disulfide bonds in the peptides apamin and endothelin could be electrochemically cleaved. Subsequent tandem MS analysis of the resulting reduced peptide ions using collision-induced dissociation (CID) and electron-capture dissociation (ECD) gave rise to extensive fragment ions, providing a fast protocol for sequencing peptides with complicated disulfide bond linkages. Flunitrazepam and clonazepam, a class of nitroaromatic drugs, are known to undergo reduction into amines which was proposed to involve nitroso and N-hydroxyl intermediates. Now in this study, these corresponding intermediate ions were successfully intercepted and their structures were confirmed by CID. This provides mass spectrometric evidence for the mechanism of the nitro to amine conversion process during nitroreduction, an important redox reaction involved in carcinogenesis. In addition, the well-known oxidation reaction of chlorpromazine was also examined. The putative transient one-electron transfer product, the chlorpromazine radical cation (m/z 318), was captured by MS, for the first time, and its structure was also verified by CID. In addition to these observations, some features of the DESI-interfaced electrochemical mass spectrometry were discussed, such as simple instrumentation and the lack of background signal. These results further demonstrate the feasibility of EC/DESI-MS for the study of the biology-relevant redox chemistry and would find applications in proteomics and drug development research.

  18. Online Investigation of Aqueous-Phase Electrochemical Reactions by Desorption Electrospray Ionization Mass Spectrometry.

    PubMed

    Lu, Mei; Liu, Yong; Helmy, Roy; Martin, Gary E; Dewald, Howard D; Chen, Hao

    2015-10-01

    Electrochemistry (EC) combined with mass spectrometry (MS) is a powerful tool for elucidation of electrochemical reaction mechanisms. However, direct online analysis of electrochemical reaction in aqueous phase was rarely explored. This paper presents the online investigation of several electrochemical reactions with biological relevance in the aqueous phase, such as nitrosothiol reduction, carbohydrate oxidation, and carbamazepine oxidation using desorption electrospray ionization mass spectrometry (DESI-MS). It was found that electroreduction of nitrosothiols [e.g., nitrosylated insulin B (13-23)] leads to free thiols by loss of NO, as confirmed by online MS analysis for the first time. The characteristic mass shift of 29 Da and the reduced intensity provide a quick way to identify nitrosylated species. Equally importantly, upon collision-induced dissociation (CID), the reduced peptide ion produces more fragment ions than its nitrosylated precursor ion (presumably the backbone fragmentation cannot compete with the facile NO loss for the precursor ion), thus facilitating peptide sequencing. In the case of saccharide oxidation, it was found that glucose undergoes electro-oxidation to produce gluconic acid at alkaline pH, but not at neutral and acidic pHs. Such a pH-dependent electrochemical behavior was also observed for disaccharides such as maltose and cellobiose. Upon electrochemical oxidation, carbamazepine was found to undergo ring contraction and amide bond cleavage, which parallels the oxidative metabolism observed for this drug in leucocytes. The mechanistic information of these redox reactions revealed by EC/DESI-MS would be of value in nitroso-proteome research and carbohydrate/drug metabolic studies.

  19. Characterization of the Cathode Electrolyte Interface in Lithium Ion Batteries by Desorption Electrospray Ionization Mass Spectrometry.

    PubMed

    Liu, Yao-Min; G Nicolau, Bruno; Esbenshade, Jennifer L; Gewirth, Andrew A

    2016-07-19

    The solid electrolyte interface (SEI) formed via electrolyte decomposition on the anode of lithium ion batteries is largely responsible for the stable cycling of conventional lithium ion batteries. Similarly, there is a lesser-known analogous layer on the cathode side of a lithium ion battery, termed the cathode electrolyte interface (CEI), whose composition and role are debated. To confirm the existence and composition of the CEI, desorption electrospray ionization mass spectrometry (DESI-MS) is applied to study common lithium ion battery cathodes. We observe CEI formation on the LiMn2O4 cathode material after cycling between 3.5 and 4.5 V vs Li/Li(+) in electrolyte solution containing 1 M LiPF6 or LiClO4 in 1:1 (v/v) ethylene carbonate (EC) and dimethyl carbonate (DMC). Intact poly(ethylene glycol) dimethyl ether is identified as the electrolyte degradation product on the cathode surface by the high mass-resolution Orbitrap mass spectrometer. When EC is paired with ethyl methyl carbonate (EMC), poly(ethylene glycol) dimethyl ether, poly(ethylene glycol) ethyl methyl ether, and poly(ethylene glycol) are found on the surface simultaneously. The presence of ethoxy and methoxy end groups indicates both methoxide and ethoxide are produced and involved in the process of oligomerization. Au surfaces cycled under different electrochemical windows as model systems for Li-ion battery anodes are also examined. Interestingly, the identical oligomeric species to those found in the CEI are found on Au surfaces after running five cycles between 2.0 and 0.1 V vs Li/Li(+) in half-cells. These results show that DESI-MS provides intact molecular information on battery electrodes, enabling deeper understanding of the SEI or CEI composition. PMID:27346184

  20. Instrumentation and method for ultrahigh resolution field desorption ionization fourier transform ion cyclotron resonance mass spectrometry of nonpolar species.

    PubMed

    Schaub, Tanner M; Hendrickson, Christopher L; Quinn, John P; Rodgers, Ryan P; Marshall, Alan G

    2005-03-01

    We describe the construction and application of a 9.4-T FT-ICR mass spectrometer interfaced to a commercial field desorption ion source for high-resolution, high-mass accuracy measurements of nonpolar species. The FT-ICR MS instrument includes a liquid injection field desorption ionization source, octopole ion guides, external octopole ion trap capable of an axial potential gradient for ion ejection, capacitively coupled open cylindrical ion trap, and pulsed gas valve for ion cooling. Model compound responses with regard to various source and instrument conditions provide a basis for interpretation of broadband mass spectra of complex mixtures. As an example, we demonstrate broadband speciation of a Gulf Coast crude oil, with respect to numerous heteroatomic classes, compound types (rings plus double bonds), and carbon number distributions.

  1. Critical factors determining the quantification capability of matrix-assisted laser desorption/ionization- time-of-flight mass spectrometry.

    PubMed

    Wang, Chia-Chen; Lai, Yin-Hung; Ou, Yu-Meng; Chang, Huan-Tsung; Wang, Yi-Sheng

    2016-10-28

    Quantitative analysis with mass spectrometry (MS) is important but challenging. Matrix-assisted laser desorption/ionization (MALDI) coupled with time-of-flight (TOF) MS offers superior sensitivity, resolution and speed, but such techniques have numerous disadvantages that hinder quantitative analyses. This review summarizes essential obstacles to analyte quantification with MALDI-TOF MS, including the complex ionization mechanism of MALDI, sensitive characteristics of the applied electric fields and the mass-dependent detection efficiency of ion detectors. General quantitative ionization and desorption interpretations of ion production are described. Important instrument parameters and available methods of MALDI-TOF MS used for quantitative analysis are also reviewed.This article is part of the themed issue 'Quantitative mass spectrometry'.

  2. Critical factors determining the quantification capability of matrix-assisted laser desorption/ionization- time-of-flight mass spectrometry.

    PubMed

    Wang, Chia-Chen; Lai, Yin-Hung; Ou, Yu-Meng; Chang, Huan-Tsung; Wang, Yi-Sheng

    2016-10-28

    Quantitative analysis with mass spectrometry (MS) is important but challenging. Matrix-assisted laser desorption/ionization (MALDI) coupled with time-of-flight (TOF) MS offers superior sensitivity, resolution and speed, but such techniques have numerous disadvantages that hinder quantitative analyses. This review summarizes essential obstacles to analyte quantification with MALDI-TOF MS, including the complex ionization mechanism of MALDI, sensitive characteristics of the applied electric fields and the mass-dependent detection efficiency of ion detectors. General quantitative ionization and desorption interpretations of ion production are described. Important instrument parameters and available methods of MALDI-TOF MS used for quantitative analysis are also reviewed.This article is part of the themed issue 'Quantitative mass spectrometry'. PMID:27644968

  3. Merits of online electrochemistry liquid sample desorption electrospray ionization mass spectrometry (EC/LS DESI MS).

    PubMed

    Looi, Wen Donq; Brown, Blake; Chamand, Laura; Brajter-Toth, Anna

    2016-03-01

    A new online electrochemistry/liquid sample desorption electrospray ionization mass spectrometry (EC/LS DESI MS) system with a simple electrochemical thin-layer flow-through cell was developed and tested using N,N-dimethyl-p-phenylenediamine (DMPA) as a model probe. Although oxidation of DMPA is observed as a result of ionization of LS in positive ion mode LS DESI, application of voltage to the online electrochemical (EC) cell in EC/LS DESI MS increases yields of oxidation products. An advantage of LS DESI MS is its sensitivity in aqueous electrolyte solutions, which improves efficiency of electrochemical reactions in EC/LS DESI MS. In highly conductive low pH aqueous buffer solutions, oxidation efficiency is close to 100%. EC/ESI MS typically requires mixed aqueous/organic solvents and low electrolyte concentrations for efficient ionization in MS, limiting efficiency of electrochemistry online with MS. Independently, the results verify higher electrochemical oxidation efficiency during positive mode ESI than during LS DESI.

  4. Efficient Methods to Generate Reproducible Mass Spectra in Matrix-Assisted Laser Desorption Ionization of Peptides

    NASA Astrophysics Data System (ADS)

    Ahn, Sung Hee; Park, Kyung Man; Bae, Yong Jin; Kim, Myung Soo

    2013-06-01

    In our previous matrix-assisted laser desorption ionization (MALDI) studies of peptides, we found that their mass spectra were virtually determined by the effective temperature in the early matrix plume, Tearly, when samples were rather homogeneous. This empirical rule allowed acquisition of quantitatively reproducible spectra. A difficulty in utilizing this rule was the complicated spectral treatment needed to get Tearly. In this work, we found another empirical rule that the total number of particles hitting the detector, or TIC, was a good measure of the spectral temperature and, hence, selection of spectra with the same TIC resulted in reproducible spectra. We also succeeded in obtaining reproducible spectra throughout a measurement by controlling TIC near a preset value through feedback adjustment of laser pulse energy. Both TIC selection and TIC control substantially reduced the shot-to-shot spectral variation in a spot, spot-to-spot variation in a sample, and even sample-to-sample variation in MALDI using α-cyano-4-hydroxycinnamic acid or 2,5-dihydroxybenzoic acid as matrix. Based on the utilization of acquired data, TIC control was more efficient than TIC selection by an order of magnitude. Both techniques produced calibration curves with excellent linearity, suggesting their utility in quantification of peptides.

  5. Metabolic Profiling Directly from the Petri Dish Using Nanospray Desorption Electrospray Ionization Imaging Mass Spectrometry

    SciTech Connect

    Watrous, Jeramie D.; Roach, Patrick J.; Heath, Brandi S.; Alexandrov, Theodore; Laskin, Julia; Dorrestein, Pieter C.

    2013-11-05

    Understanding molecular interaction pathways in complex biological systems constitutes a treasure trove of knowledge that might facilitate the specific, chemical manipulation of the countless microbiological systems that occur throughout our world. However, there is a lack of methodologies that allow the direct investigation of chemical gradients and interactions in living biological systems, in real time. Here, we report the use of nanospray desorption electrospray ionization (nanoDESI) imaging mass spectrometry for in vivo metabolic profiling of living bacterial colonies directly from the Petri dish with absolutely no sample preparation needed. Using this technique, we investigated single colonies of Shewanella oneidensis MR-1, Bacillus subtilis 3610, and Streptomyces coelicolor A3(2) as well as a mixed biofilm of S. oneidensis MR-1 and B. subtilis 3610. Data from B. subtilis 3610 and S. coelicolor A3(2) provided a means of validation for the method while data from S. oneidensis MR-1 and the mixed biofilm showed a wide range of compounds that this bacterium uses for the dissimilatory reduction of extracellular metal oxides, including riboflavin, iron-bound heme and heme biosynthetic intermediates, and the siderophore putrebactin.

  6. Chemical Analysis of Organic Aerosols Using Reactive Nanospray Desorption Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Laskin, A.; Laskin, J.; Nizkorodov, S.

    2013-12-01

    Nanospray Desorption Electrospray Ionization (nano-DESI) technique integrated with high resolution mass spectrometry (HR-MS) enables molecular level analysis of organic aerosol (OA) samples. In nano-DESI, analyte is desorbed into a small volume solvent bridge formed between two capillaries positioned in contact with analyte and enables fast and efficient characterization of OA collected on substrates without sample preparation. We report applications of the nano-DESI/HR-MS approach in a number of our recent studies focused on molecular identification of organic compounds in laboratory and in field collected OA samples. Reactive nano-DESI approach where selected reagent is added to the solvent is used for examining the presence of individual species containing specific functional groups and for their quantification within complex mixtures of OA. Specifically, we use the Girard's reagent T (GT) to probe and quantify carbonyl compounds in the SOA mixtures. We estimate for the first time the amounts of dimers and trimers in the SOA mixtures. We found that the most abundant dimer in limonene/O3 SOA was detected at the ˜0.5 pg level and the total amount of dimers and trimers in the analyzed sample was ˜11 pg. Understanding of the OA composition at the molecular level allowed us to identify key aging reactions, including the transformation of carbonyls to imines and carbonyl-imine oligomerization, that may contribute to the formation of brown carbon in the atmosphere.

  7. Direct detection of chloramphenicol in honey by neutral desorption-extractive electrospray ionization mass spectrometry.

    PubMed

    Huang, X Y; Fang, X W; Zhang, X; Dai, X M; Guo, X L; Chen, H W; Luo, L P

    2014-11-01

    Herein, we constructed a platform of neutral desorption-extractive electrospray ionization mass spectrometry (ND-EESI-MS) for direct and rapid detection of chloramphenicol (CAP) in honey samples diluted with methanol. Under the optimized working conditions, the quantitative information of CAP residues was acquired effectively by EESI-Ion Trap MS (n) . Using heated methanol-N2 as spray reagent, we reduced the limit of determination (LOD) from 73.3 ng/mL to 0.3 ng/mL, and the CAP detection is linear in the range of 1-5000 ng/mL (R = 0.9947). For the honey samples with CAP of 10, 100, and 1000 ng/mL, the recoveries were 133.0, 80.6, and 101.1%, and the relative standard deviations were 5.96, 8.82, and 8.71%, respectively. The reproducibility assays showed the stability of this method. Therefore, this ND-EESI-MS method is powerful for direct, rapid, and quantitative CAP analysis in honey samples with high sensitivity, precision, and specificity. PMID:25277102

  8. Thermal desorption gas chromatography with mass spectrometry study of outgassing from polymethacrylimide foam (Rohacell®).

    PubMed

    Carrasco-Correa, Enrique J; Herrero-Martínez, José M; Consuegra, Lina; Ramis-Ramos, Guillermo; Sanz, Rafael Mata; Martínez, Benito Gimeno; Esbert, Vicente E Boria; García-Baquero, David Raboso

    2015-09-01

    Polymethacrylimide foams are used as light structural materials in outer-space devices; however, the foam closed cells contain volatile compounds that are outgassed even at low temperatures. These compounds ignite as plasmas under outer-space radiation and the intense radio-frequency fields used in communications. Since plasmas may cause spacecraft fatal events, the conditions in which they are ignited should be investigated. Therefore, qualitative and quantitative knowledge about polymethacrylimide foam outgassing should be established. Using thermogravimetric analysis, weight losses reached 3% at ca. 200°C. Thermal desorption gas chromatography with mass spectrometry detection was used to study the offgassed compounds. Using successive 4 min heating cycles at 125°C, each one corresponding to an injection, significant amounts of nitrogen (25.3%), water (2.6%), isobutylene (11.3%), tert-butanol (2.9%), 1-propanol (11.9%), hexane (25.3%), propyl methacrylate (1.4%), higher hydrocarbons (11.3%), fatty acids (2.2%) and their esters (1.3%), and other compounds were outgassed. Other compounds were observed during the main stage of thermal destruction (220-280°C). A similar study at 175°C revealed the extreme difficulty in fully outgassing polar compounds from polymethacrylimide foams by baking and showed the different compositions of the offgassed atmosphere that can be expected in the long term. PMID:26106018

  9. Rapid determination of nicotine in urine by direct thermal desorption ion trap mass spectrometry

    SciTech Connect

    Wise, M.B.; Ilgner, R.H.; Guerin, M.R.

    1990-01-01

    The measurement of nicotine and cotinine in physiological fluids (urine, blood serum, and saliva) is widely used as a means of assessing human exposure to environmental tobacco smoke (ETS). Although numerous analytical methods exist for these measurements, they generally involve extensive sample preparation which increases cost and decreases sample throughput. We report the use of thermal desorption directly into an ion trap mass spectrometer (ITMS) for the rapid determination of nicotine and cotinine in urine. A 1{mu}L aliquot of urine is injected into a specially designed inlet and flash vaporized directly into an ITMS through an open-split capillary restrictor interface. Isobutane chemical ionization is used to generate (M+H){sup +} ions of the analytes and collision induced dissociation is used to generate characteristic fragment ions which are used to confirm their identity. Quantification is achieved by integrating the ion current for the characteristic ions and comparing with an external working curve. Detection limits are approximately 50 pg per analyte and the sample turnaround time is approximately 3 minutes without the need for extensive sample preparation. 12 refs., 5 figs.

  10. Neutral desorption extractive electrospray ionization mass spectrometry for fast screening sunscreen agents in cream cosmetic products.

    PubMed

    Zhang, Xinglei; Liu, Yan; Zhang, Jinghua; Hu, Zhong; Hu, Bin; Ding, Liying; Jia, Li; Chen, Huanwen

    2011-09-15

    High throughput analysis of sunscreen agents present in cream cosmetic has been demonstrated, typically 2 samples per minute, using neutral desorption extractive electrospray ionization mass spectrometry (ND-EESI-MS) without sample pretreatment. For the targeted compounds such as 4-Aminobenzoic acid and oxybenzone, ND-EESI-MS method provided linear signal responses in the range of 1-100 ppb. Limits of detection (LOD) of the method were estimated at sub-ppb levels for the analytes tested. Reasonable relative standard deviation (RSD=8.4-16.0%) was obtained as a result of 10 independent measurements for commercial cosmetics samples spiked with each individual sunscreen agents at 1-10 ppb. Acceptable recoveries were achieved in the range of 87-116% for direct analysis of commercial cream cosmetic samples. The experimental data demonstrate that ND-EESI-MS is a useful tool for high throughput screening of sunscreen agents in highly viscous cream cosmetic products, with the capability to obtain quantitative information of the analytes.

  11. Tracing origins of complex pharmaceutical preparations using surface desorption atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Zhang, Xinglei; Jia, Bin; Huang, Keke; Hu, Bin; Chen, Rong; Chen, Huanwen

    2010-10-01

    A novel strategy to trace the origins of commercial pharmaceutical products has been developed based on the direct chemical profiling of the pharmaceutical products by surface desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS). Besides the unambiguous identification of active drug components, various compounds present in the matrixes are simultaneously detected without sample pretreatment, providing valuable information for drug quality control and origin differentiation. Four sources of commercial amoxicillin products made by different manufacturers have been successfully differentiated. This strategy has been extended to secerning six sources of Liuwei Dihuang Teapills, which are herbal medicine preparations with extremely complex matrixes. The photolysis status of chemical drug products and the inferior natural herd medicine products prepared with different processes (e.g., extra heating) were also screened using the method reported here. The limit of detection achieved in the MS/MS experiments was estimated to be 1 ng/g for amoxicillin inside the capsule product. Our experimental data demonstrate that DAPCI-MS is a useful tool for rapid pharmaceutical analysis, showing promising perspectives for tracking the entire pharmaceutical supply chain to prevent counterfeit intrusions.

  12. Imaging Nicotine in Rat Brain Tissue by Use of Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Lanekoff, Ingela T.; Thomas, Mathew; Carson, James P.; Smith, Jordan N.; Timchalk, Charles; Laskin, Julia

    2013-01-15

    Imaging mass spectrometry offers simultaneous detection of drugs, drug metabolites and endogenous substances in a single experiment. This is important when evaluating effects of a drug on a complex organ system such as the brain, where there is a need to understand how regional drug distribution impacts function. Nicotine is an addictive drug and its action in the brain is of high interest. Here we use nanospray desorption electrospray ionization, nano-DESI, imaging to discover the localization of nicotine in rat brain tissue after in vivo administration of nicotine. Nano-DESI is a new ambient technique that enables spatially-resolved analysis of tissue samples without special sample pretreatment. We demonstrate high sensitivity of nano-DESI imaging that enables detection of only 0.7 fmole nicotine per pixel in the complex brain matrix. Furthermore, by adding deuterated nicotine to the solvent, we examined how matrix effects, ion suppression, and normalization affect the observed nicotine distribution. Finally, we provide preliminary results suggesting that nicotine localizes to the hippocampal substructure called dentate gyrus.

  13. Direct analysis of ethylenediaminetetraacetic acid (EDTA) on concrete by reactive-desorption electrospray ionization mass spectrometry.

    PubMed

    Lebeau, D; Reiller, P E; Lamouroux, C

    2015-01-01

    Analysis of organic ligands such as ethylenediaminetetraacetic acid (EDTA) is today an important challenge due to their ability to increase the mobility of radionuclides and metals. Reactive desorption electrospray ionization mass spectrometry (reactive-DESI-MS) was used for direct analysis of EDTA on concrete samples. EDTA forms complexes and those with Fe(III) ions are among the most thermodynamically favored. This complexing capacity was used to improve the specific detection of EDTA directly on a concrete matrix by doping the solvent spray of DESI with a solution of FeCl3 to selectively create the complex between EDTA and Fe(III). Thus, EDTA sensitivity was largely improved by two orders of magnitude with reactive-DESI-MS experiments thanks to the specific detection of EDTA as a [EDTA-4H+Fe(III)](-) complex. The proof of principle that reactive DESI can be applied to concrete samples to detect EDTA has been demonstrated. Its capacity for semi-quantitative determination and localization of EDTA under ambient conditions and with very little sample preparation, minimizing sample manipulations and solvent volumes, two important conditions for the development of new methodologies in the field of analytical chemistry, has been shown.

  14. Desorption electrospray ionization mass spectrometry reveals surface-mediated antifungal chemical defense of a tropical seaweed

    PubMed Central

    Lane, Amy L.; Nyadong, Leonard; Galhena, Asiri S.; Shearer, Tonya L.; Stout, E. Paige; Parry, R. Mitchell; Kwasnik, Mark; Wang, May D.; Hay, Mark E.; Fernandez, Facundo M.; Kubanek, Julia

    2009-01-01

    Organism surfaces represent signaling sites for attraction of allies and defense against enemies. However, our understanding of these signals has been impeded by methodological limitations that have precluded direct fine-scale evaluation of compounds on native surfaces. Here, we asked whether natural products from the red macroalga Callophycus serratus act in surface-mediated defense against pathogenic microbes. Bromophycolides and callophycoic acids from algal extracts inhibited growth of Lindra thalassiae, a marine fungal pathogen, and represent the largest group of algal antifungal chemical defenses reported to date. Desorption electrospray ionization mass spectrometry (DESI-MS) imaging revealed that surface-associated bromophycolides were found exclusively in association with distinct surface patches at concentrations sufficient for fungal inhibition; DESI-MS also indicated the presence of bromophycolides within internal algal tissue. This is among the first examples of natural product imaging on biological surfaces, suggesting the importance of secondary metabolites in localized ecological interactions, and illustrating the potential of DESI-MS in understanding chemically-mediated biological processes. PMID:19366672

  15. Design, fabrication and test of a microfluidic nebulizer chip for desorption electrospray ionization mass spectrometry

    PubMed Central

    Sen, A K; Darabi, J; Knapp, D R

    2009-01-01

    This paper presents design, microfabrication, and test of a microfluidic nebulizer chip for desorption electrospray ionization mass spectrometry (DESI-MS) in proteomic analysis. The microfluidic chip is fabricated using cyclic olefin copolymer (COC) substrates. The fluidic channels are thermally embossed onto a base substrate using a nickel master and then a top substrate is thermally bonded to seal the channels. Carbon ink embossed into the top COC substrate is used to established electrical connection between the external power supply and the liquid in the channel. The microfluidic chip to external capillary connection is fabricated using Nanoport™ interconnection system. Preliminary leakage test was performed to demonstrate the interconnection system is leak-free and pressure test was performed to evaluate the burst pressure. Finally, the nebulizer chip was used to perform DESI-MS for analyzing peptides (BSA and bradykinin) and reserpine on the nanoporous alumina surface. DESI-MS performance of the microfluidic nebulizer chip is compared with that obtained using a conventional DESI nebulizer. PMID:20161284

  16. Laser-Induced Acoustic Desorption/Atmospheric Pressure Chemical Ionization Mass Spectrometry

    PubMed Central

    Gao, Jinshan; Borton, David J.; Owen, Benjamin C.; Jin, Zhicheng; Hurt, Matt; Amundson, Lucas M.; Madden, Jeremy T.; Qian, Kuangnan; Kenttämaa, Hilkka I.

    2010-01-01

    Laser-induced acoustic desorption (LIAD) was successfully coupled to a conventional atmospheric pressure chemical ionization (APCI) source in a linear quadrupole ion trap mass spectrometer (LQIT). Model compounds representing a wide variety of different types, including basic nitrogen and oxygen compounds, aromatic and aliphatic compounds, as well as unsaturated and saturated hydrocarbons, were tested separately and as a mixture. These model compounds were successfully evaporated into the gas phase by using LIAD and then ionized by using APCI with different reagents. Four APCI reagent systems were tested: the traditionally used mixture of methanol and water, neat benzene, neat carbon disulfide, and nitrogen gas (no liquid reagent). The mixture of methanol and water produced primarily protonated molecules, as expected. However, only the most basic compounds yielded ions under these conditions. In sharp contrast, using APCI with either neat benzene or neat carbon disulfide as the reagent resulted in the ionization of all the analytes studied to predominantly yield stable molecular ions. Benzene yielded a larger fraction of protonated molecules than carbon disulfide, which is a disadvantage. A similar amount of fragmentation was observed for these reagents. When the experiment was performed without a liquid reagent(nitrogen gas was the reagent), more fragmentation was observed. Analysis of a known mixture as well as a petroleum cut was also carried out. In summary, the new experiment presented here allows the evaporation of thermally labile compounds, both polar and nonpolar, without dissociation or aggregation, and their ionization to form stable molecular ions. PMID:21472571

  17. Thermal desorption gas chromatography with mass spectrometry study of outgassing from polymethacrylimide foam (Rohacell®).

    PubMed

    Carrasco-Correa, Enrique J; Herrero-Martínez, José M; Consuegra, Lina; Ramis-Ramos, Guillermo; Sanz, Rafael Mata; Martínez, Benito Gimeno; Esbert, Vicente E Boria; García-Baquero, David Raboso

    2015-09-01

    Polymethacrylimide foams are used as light structural materials in outer-space devices; however, the foam closed cells contain volatile compounds that are outgassed even at low temperatures. These compounds ignite as plasmas under outer-space radiation and the intense radio-frequency fields used in communications. Since plasmas may cause spacecraft fatal events, the conditions in which they are ignited should be investigated. Therefore, qualitative and quantitative knowledge about polymethacrylimide foam outgassing should be established. Using thermogravimetric analysis, weight losses reached 3% at ca. 200°C. Thermal desorption gas chromatography with mass spectrometry detection was used to study the offgassed compounds. Using successive 4 min heating cycles at 125°C, each one corresponding to an injection, significant amounts of nitrogen (25.3%), water (2.6%), isobutylene (11.3%), tert-butanol (2.9%), 1-propanol (11.9%), hexane (25.3%), propyl methacrylate (1.4%), higher hydrocarbons (11.3%), fatty acids (2.2%) and their esters (1.3%), and other compounds were outgassed. Other compounds were observed during the main stage of thermal destruction (220-280°C). A similar study at 175°C revealed the extreme difficulty in fully outgassing polar compounds from polymethacrylimide foams by baking and showed the different compositions of the offgassed atmosphere that can be expected in the long term.

  18. Enhancement of the molecular ion yield in plasma desorption mass spectrometry using explosive matrices.

    PubMed

    Zubarev, R A; Håkansson, P; Sundqvist, B; Talrose, V L

    1997-01-01

    The working hypothesis of this study was that the chemical energy of matrix material may be released, although only on a microscale, under MeV ion bombardment and may assist ejection of large intact bioorganic molecules. To test the hypothesis, the performance of several common explosives, as matrices in plasma desorption mass spectrometry, was compared to the standard matrix, nitrocellulose (NC), which is also a high explosive. Two explosives, RDX and HMX, were found to be new, effective matrices for peptides and proteins. While the performance of RDX was comparable with that of nitrocellulose, HMX gave a superior molecular ion yield and a higher average charge state of desorbed molecular ions compared with NC. Noth RDX and HMX have a similar chemical composition and structure, although the latter is a more powerful explosive. The measured total ion yield allows the conclusion that the increase in the amount of ejected material, due to the chemical energy release in high explosives under MeV ion bombardment, is limited, perhaps to a factor of 2 to 3. The fact that not all tested explosives gave molecular ions from peptides and proteins suggests that other factors, such as gas-phase chemistry, may play a significant role in molecular ion formation.

  19. Enhanced capabilities for imaging gangliosides in murine brain with matrix-assisted laser desorption/ionization and desorption electrospray ionization mass spectrometry coupled to ion mobility separation.

    PubMed

    Škrášková, Karolina; Claude, Emmanuelle; Jones, Emrys A; Towers, Mark; Ellis, Shane R; Heeren, Ron M A

    2016-07-15

    The increased interest in lipidomics calls for improved yet simplified methods of lipid analysis. Over the past two decades, mass spectrometry imaging (MSI) has been established as a powerful technique for the analysis of molecular distribution of a variety of compounds across tissue surfaces. Matrix-assisted laser desorption/ionization (MALDI) MSI is widely used to study the spatial distribution of common lipids. However, a thorough sample preparation and necessity of vacuum for efficient ionization might hamper its use for high-throughput lipid analysis. Desorption electrospray ionization (DESI) is a relatively young MS technique. In DESI, ionization of molecules occurs under ambient conditions, which alleviates sample preparation. Moreover, DESI does not require the application of an external matrix, making the detection of low mass species more feasible due to the lack of chemical matrix background. However, irrespective of the ionization method, the final information obtained during an MSI experiment is very complex and its analysis becomes challenging. It was shown that coupling MSI to ion mobility separation (IMS) simplifies imaging data interpretation. Here we employed DESI and MALDI MSI for a lipidomic analysis of the murine brain using the same IMS-enabled instrument. We report for the first time on the DESI IMS-MSI of multiply sialylated ganglioside species, as well as their acetylated versions, which we detected directly from the murine brain tissue. We show that poly-sialylated gangliosides can be imaged as multiply charged ions using DESI, while they are clearly separated from the rest of the lipid classes based on their charge state using ion mobility. This represents a major improvement in MSI of intact fragile lipid species. We additionally show that complementary lipid information is reached under particular conditions when DESI is compared to MALDI MSI.

  20. Atmospheric pressure glow discharge desorption mass spectrometry for rapid screening of pesticides in food.

    PubMed

    Jecklin, Matthias Conradin; Gamez, Gerardo; Touboul, David; Zenobi, Renato

    2008-09-01

    Flowing afterglow atmospheric pressure glow discharge tandem mass spectrometry (APGD-MS/MS) is used for the analysis of trace amounts of pesticides in fruit juices and on fruit peel. The APGD source was rebuilt after Andrade et al. (Andrade et al., Anal. Chem. 2008; 80: 2646-2653; 2654-2663) and mounted onto a hybrid quadrupole time-of-flight mass spectrometer. Apple, cranberry, grape and orange juices as well as fruit peel and salad leaves were spiked with aqueous solutions containing trace amounts of the pesticides alachlor, atrazine, carbendazim, carbofuran, dinoseb, isoproturon, metolachlor, metolcarb, propoxur and simazine. Best limits of determination (LODs) of pesticides in the fruit juices were achieved for metolcarb (1 microg/L in apple juice), carbofuran and dinoseb (2 microg/L in apple juice); for the analysis of apple skin best LODs were 10 pg/cm(2) of atrazine, metolcarb and propoxur which corresponds to an estimated concentration of 0.01 microg/kg apple, taking into account the surface area and the weight of the apple. The measured LODs were within or below the allowed maximum residue levels (MRLs) decreed by the European Union (1-500 microg/kg for pesticides in fruit juice and 0.01-5 microg/kg for apple skin). No sample pretreatment (extraction, pre-concentration, chromatographic separation) was necessary to analyze these pesticides by direct desorption/ionization using APGD-MS and to identify them using MS/MS. This makes APGD-MS a powerful high-throughput tool for the investigation of very low amounts of pesticides in fruit juices and on fruit peel/vegetable skin. PMID:18697232

  1. Structural features of lipoarabinomannan from Mycobacterium bovis BCG. Determination of molecular mass by laser desorption mass spectrometry.

    PubMed

    Venisse, A; Berjeaud, J M; Chaurand, P; Gilleron, M; Puzo, G

    1993-06-15

    It was recently shown that mycobacterial lipoarabinomannan (LAM) can be classified into two types (Chatterjee, D., Lowell, K., Rivoire B., McNeil M. R., and Brennan, P. J. (1992) J. Biol. Chem. 267, 6234-6239) according to the presence or absence of mannosyl residues (Manp) located at the nonreducing end of the oligoarabinosyl side chains. These two types of LAM were found in a pathogenic Mycobacterium tuberculosis strain and in an avirulent M. tuberculosis strain, respectively, suggesting that LAM with Manp characterizes virulent and "disease-inducing strains." We now report the structure of the LAM from Mycobacterium bovis Bacille Calmette-Guérin (BCG) strain Pasteur, largely used throughout the world as vaccine against tuberculosis. Using an up-to-date analytical approach, we found that the LAM of M. bovis BCG belongs to the class of LAMs capped with Manp. By means of two-dimensional homonuclear and heteronuclear scalar coupling NMR analysis and methylation data, the sugar spin system assignments were partially established, revealing that the LAM contained two types of terminal Manp and 2-O-linked Manp. From the following four-step process: (i) partial hydrolysis of deacylated LAM (dLAM), (ii) oligosaccharide derivatization with aminobenzoic ethyl ester, (iii) HPLC purification, (iv) FAB/MS-MS analysis; it was shown that the dimannosyl unit alpha-D-Manp-(1-->2)-alpha-D-Manp is the major residue capping the termini of the arabinan of the LAM. In this report, LAM molecular mass determination was established using matrix-assisted UV-laser desorption/ionization mass spectrometry which reveals that the LAM molecular mass is around 17.4 kDa. The similarity of the LAM structures between M. bovis BCG and M. tuberculosis H37Rv is discussed in regard to their function in the immunopathology of mycobacterial infection.

  2. Matrix-assisted laser-desorption-ionization mass spectrometry of proteins using a free-electron laser

    SciTech Connect

    Cramer, R.; Hillenkamp, F.; Haglund, R.

    1995-12-31

    Matrix-assisted laser desorption-ionization (MALDI) mass spectrometry (MS) is one of the most promising techniques for spectral fingerprinting large molecules, such as proteins, oligonucleotides and carbohydrates. In the usual implementation of this technique, the analyte molecule is dissolved in an aromatic liquid matrix material which resonantly absorbs ultraviolet laser light. Resonant absorption by {pi}-{pi}* transitions volatilizes the matrix and initiates subsequent charge transfer to the analyte molecules, which are detected by time-of-flight mass spectrometry. Recent MALDI-MS studies with Er:YAG (2.94 {mu}m) and CO{sub 2}{sup 4} (9.4-10.6 {mu}m) lasers suggest that them is significant unexplored potential for mass spectrometry of macromolecules, including oligonucleotide, in the mid-infrared. Preliminary experiments show that it is possible to capitalize on the rich rovibronic absorption spectrum of virtually all organics to initiate resonant desorption in matrix material over the entire range of pH values. However, the mechanism of charge transfer is particularly problematic for infrared MALDI because of the low photon energy. In this paper, we report the results of MALI-MS studies on small proteins using the Vanderbilt FEL and several matrix materials. Proteins with masses up to roughly 6,000 amu were detected with high resolution in a linear time-of-flight mass spectrometer. By varying the pulse duration using a broadband Pockels cell, we have been able to compare the results of relatively long (5 {mu}s) and short (0.1 {mu}s) irradiation on the desorption and ionization processes. Compared to uv-MALDI spectra of identical analytes obtained with a nitrogen laser (337 nm) in the same time-of-flight spectrometer, the infrared results appear to show that the desorption and ionization process goes on over a somewhat longer time scale.

  3. Analysis of colorectal adenocarcinoma tissue by desorption electrospray ionization mass spectrometric imaging.

    PubMed

    Gerbig, Stefanie; Golf, Ottmar; Balog, Julia; Denes, Julia; Baranyai, Zsolt; Zarand, Attila; Raso, Erzsebet; Timar, Jozsef; Takats, Zoltan

    2012-06-01

    Negative ion desorption electrospray ionization (DESI) was used for the analysis of an ex vivo tissue sample set comprising primary colorectal adenocarcinoma samples and colorectal adenocarcinoma liver metastasis samples. Frozen sections (12 μm thick) were analyzed by means of DESI imaging mass spectrometry (IMS) with spatial resolution of 100 μm using a computer-controlled DESI imaging stage mounted on a high resolution Orbitrap mass spectrometer. DESI-IMS data were found to predominantly feature complex lipids, including phosphatidyl-inositols, phophatidyl-ethanolamines, phosphatidyl-serines, phosphatidyl-ethanolamine plasmalogens, phosphatidic acids, phosphatidyl-glycerols, ceramides, sphingolipids, and sulfatides among others. Molecular constituents were identified based on their exact mass and MS/MS fragmentation spectra. An identified set of molecules was found to be in good agreement with previously reported DESI imaging data. Different histological tissue types were found to yield characteristic mass spectrometric data in each individual section. Histological features were identified by comparison to hematoxylin-eosin stained neighboring sections. Ions specific to certain histological tissue types (connective tissue, smooth muscle, healthy mucosa, healthy liver parenchyma, and adenocarcinoma) were identified by semi-automated screening of data. While each section featured a number of tissue-specific species, no potential global biomarker was found in the full sample set for any of the tissue types. As an alternative approach, data were analyzed by principal component analysis (PCA) and linear discriminant analysis (LDA) which resulted in efficient separation of data points based on their histological types. A pixel-by-pixel tissue identification method was developed, featuring the PCA/LDA analysis of authentic data set, and localization of unknowns in the resulting 60D, histologically assigned LDA space. Novel approach was found to yield results which are

  4. Nanostructured weathering steel for matrix-free laser desorption ionisation mass spectrometry and imaging of metabolites, drugs and complex glycans.

    PubMed

    Etxebarria, Juan; Calvo, Javier; Reichardt, Niels-Christian

    2014-06-01

    Weathering steel has been employed for the first time to prepare sample plates for matrix-free laser desorption ionisation mass spectrometry (LDI-MS) of small molecules up to a mass range of around 1500 Da. The effective UV absorption, heat conductivity and porosity of the nanostructured inner rust layer formed during passivation determine the excellent performance in LDI-MS for a broad range of different analyte classes. The inexpensive material was evaluated in a series of relevant analytical applications ranging from the matrix-free detection of serum metabolites, lactose quantification, lipid analysis in milk to the glycoprofiling of antibodies and imaging mass spectrometry of brain tissue samples. PMID:24737011

  5. The Effect of Culture Conditions on Microorganism Identification by Matrix-Assisted Laser Desorption Ionization Mass Spectrometry

    SciTech Connect

    Valentine, Nancy B.; Wunschel, Sharon C.; Wunschel, David S.; Petersen, Catherine E.; Wahl, Karen L.

    2005-01-01

    Abstract Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been used to identify bacteria based upon protein signatures. This research shows that while some different proteins are produced by vegetative bacteria when they are cultured in different growth media, positive identification with MALDI-TOF MS is still possible with the protocol established at Pacific Northwest National Laboratory (PNNL)(11). A core set of small proteins remain constant under at least four different culture media conditions including minimal medium -M9, rich media - tryptic soy broth (TSB) or Luria-Bertani (LB) broth and blood agar plates such that analysis of the intact cells by matrix-assisted laser desorption/ionization mass spectrometry allows for consistent identification.

  6. Workplace monitoring for volatile organic compounds using thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Grote, Ardith A; Kennedy, Eugene R

    2002-10-01

    The interest in the identification of volatile organic compounds in the workplace has been a major focus of many National Institute for Occupational Safety and Health (NIOSH) field studies. A primary technique for sampling and analysis of these compounds is summarized by NIOSH Manual of Analytical Methods (NMAM) 2549. This is a screening method that uses a multi-bed sorbent to trap a wide variety of compounds and compound classes. Thermal desorption techniques are used as a first attempt to characterize potential contaminants in a workplace and to determine what future sampling and analyses must be performed. Field examples are provided to show the versatility of thermal desorption methods and techniques. Due to their sensitivity, thermal desorption tube methods are sometimes required in order to measure the workplace concentrations of unusual compounds. In other situations, the exposures are too high or varied to make thermal desorption tubes practical. In these cases, the identification of contaminants with thermal desorption tubes leads to new method developments for the quantification of specific compounds using more conventional solid sorbent-solvent desorption based methods.

  7. Development of matrix-assisted ultraviolet laser desorption/ionization mass spectrometry for the structural analysis of glycoproteins

    SciTech Connect

    Chevrier, M.R.

    1993-01-01

    This thesis describes the design, construction and characterization of an ultraviolet laser desorption time-of-flight [TOF] mass spectrometer and its subsequent application to glycoprotein structural analysis utilizing matrix-assisted laser desorption/ionization [MALDI] mass spectrometry. At the inception of this work, commercial mass spectrometers utilizing MALDI were not available, and most reports of the phenomena utilized the 266 nm wavelength provided by frequency-quadrupled Nd:YAG lasers. This work involved the design and construction of a high-voltage-extraction linear TOF mass analyzer equipped with a multiple sample inlet system and a 337 manometer, 600 picosecond pulsed nitrogen laser. In MALDI the [open quotes]matrix[close quotes], a strong absorber of a laser wavelength, is co-crystallized with the analyte. The laser photons absorbed by the matrix lead to ionization of the analyte and subsequent desorption from the surface into the gas phase. While nicotinic acid and caffeic acid were reported as effective matrices at 266 and 355 nm, respectively, several other matrices were examined for their efficiency at 337 nm, including [alpha]-cyano-4-hydroxy cinnamic acid and gentisic acid, which proved to be advantageous for glycoconjugate analysis. Glycoproteins, phosphoproteins, nucleic acids, and proteolytic digests were all successfully analyzed using the pulsed nitrogen laser. Analysis of numerous peptides and proteins demonstrated femtomolar sensitivity, mass range in excess of 350 kiloDaltons, mass resolution circa 700, and mass accuracy better than 0.1%. The completed instrument was utilized to analyze glycopeptides for carbohydrate sites and microheterogeneity, by performing MALDI mass spectrometry [MALDI/MS] following enzymatic and chemical reactions. In many cases, unfractionated or partially fractionated mixtures were analyzed directly thereby reducing preparative chromatography.

  8. Rapid Detection of OXA-48-Producing Enterobacteriaceae by Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry.

    PubMed

    Oviaño, Marina; Barba, Maria José; Fernández, Begoña; Ortega, Adriana; Aracil, Belén; Oteo, Jesús; Campos, José; Bou, Germán

    2016-03-01

    A rapid and sensitive (100%) matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) assay was developed to detect OXA-48-type producers, using 161 previously characterized clinical isolates. Ertapenem was monitored to detect carbapenem resistance, and temocillin was included in the assay as a marker for OXA-48-producers. Structural analysis of temocillin is described. Data are obtained within 60 min. PMID:26677247

  9. Fusobacterium nucleatum subspecies identification by matrix-assisted laser desorption ionization-time of flight mass spectrometry.

    PubMed

    Nie, Shuping; Tian, Baoyu; Wang, Xiaowei; Pincus, David H; Welker, Martin; Gilhuley, Kathleen; Lu, Xuedong; Han, Yiping W; Tang, Yi-Wei

    2015-04-01

    We explored the use of matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) for identification of Fusobacterium nucleatum subspecies. MALDI-TOF MS spectra of five F. nucleatum subspecies (animalis, fusiforme, nucleatum, polymorphum, and vincentii) were analyzed and divided into four distinct clusters, including subsp. animalis, nucleatum, polymorphum, and fusiforme/vincentii. MALDI-TOF MS with the modified SARAMIS database further correctly identified 28 of 34 F. nucleatum clinical isolates to the subspecies level.

  10. Rapid Detection of OXA-48-Producing Enterobacteriaceae by Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry.

    PubMed

    Oviaño, Marina; Barba, Maria José; Fernández, Begoña; Ortega, Adriana; Aracil, Belén; Oteo, Jesús; Campos, José; Bou, Germán

    2016-03-01

    A rapid and sensitive (100%) matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) assay was developed to detect OXA-48-type producers, using 161 previously characterized clinical isolates. Ertapenem was monitored to detect carbapenem resistance, and temocillin was included in the assay as a marker for OXA-48-producers. Structural analysis of temocillin is described. Data are obtained within 60 min.

  11. Rapid Detection of OXA-48-Producing Enterobacteriaceae by Matrix-Assisted Laser Desorption Ionization−Time of Flight Mass Spectrometry

    PubMed Central

    Oviaño, Marina; Barba, Maria José; Fernández, Begoña; Ortega, Adriana; Aracil, Belén; Oteo, Jesús; Campos, José

    2015-01-01

    A rapid and sensitive (100%) matrix-assisted laser desorption ionization−time of flight mass spectrometry (MALDI-TOF MS) assay was developed to detect OXA-48-type producers, using 161 previously characterized clinical isolates. Ertapenem was monitored to detect carbapenem resistance, and temocillin was included in the assay as a marker for OXA-48-producers. Structural analysis of temocillin is described. Data are obtained within 60 min. PMID:26677247

  12. Measurement of volatile plant compounds in field ambient air by thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Cai, Xiao-Ming; Xu, Xiu-Xiu; Bian, Lei; Luo, Zong-Xiu; Chen, Zong-Mao

    2015-12-01

    Determination of volatile plant compounds in field ambient air is important to understand chemical communication between plants and insects and will aid the development of semiochemicals from plants for pest control. In this study, a thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method was developed to measure ultra-trace levels of volatile plant compounds in field ambient air. The desorption parameters of TD, including sorbent tube material, tube desorption temperature, desorption time, and cold trap temperature, were selected and optimized. In GC-MS analysis, the selected ion monitoring mode was used for enhanced sensitivity and selectivity. This method was sufficiently sensitive to detect part-per-trillion levels of volatile plant compounds in field ambient air. Laboratory and field evaluation revealed that the method presented high precision and accuracy. Field studies indicated that the background odor of tea plantations contained some common volatile plant compounds, such as (Z)-3-hexenol, methyl salicylate, and (E)-ocimene, at concentrations ranging from 1 to 3400 ng m(-3). In addition, the background odor in summer was more abundant in quality and quantity than in autumn. Relative to previous methods, the TD-GC-MS method is more sensitive, permitting accurate qualitative and quantitative measurements of volatile plant compounds in field ambient air. PMID:26493981

  13. Measurement of volatile plant compounds in field ambient air by thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Cai, Xiao-Ming; Xu, Xiu-Xiu; Bian, Lei; Luo, Zong-Xiu; Chen, Zong-Mao

    2015-12-01

    Determination of volatile plant compounds in field ambient air is important to understand chemical communication between plants and insects and will aid the development of semiochemicals from plants for pest control. In this study, a thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method was developed to measure ultra-trace levels of volatile plant compounds in field ambient air. The desorption parameters of TD, including sorbent tube material, tube desorption temperature, desorption time, and cold trap temperature, were selected and optimized. In GC-MS analysis, the selected ion monitoring mode was used for enhanced sensitivity and selectivity. This method was sufficiently sensitive to detect part-per-trillion levels of volatile plant compounds in field ambient air. Laboratory and field evaluation revealed that the method presented high precision and accuracy. Field studies indicated that the background odor of tea plantations contained some common volatile plant compounds, such as (Z)-3-hexenol, methyl salicylate, and (E)-ocimene, at concentrations ranging from 1 to 3400 ng m(-3). In addition, the background odor in summer was more abundant in quality and quantity than in autumn. Relative to previous methods, the TD-GC-MS method is more sensitive, permitting accurate qualitative and quantitative measurements of volatile plant compounds in field ambient air.

  14. Visualizing metabolite distribution and enzymatic conversion in plant tissues by desorption electrospray ionization mass spectrometry imaging.

    PubMed

    Li, Bin; Knudsen, Camilla; Hansen, Natascha Krahl; Jørgensen, Kirsten; Kannangara, Rubini; Bak, Søren; Takos, Adam; Rook, Fred; Hansen, Steen H; Møller, Birger Lindberg; Janfelt, Christian; Bjarnholt, Nanna

    2013-06-01

    In comparison with the technology platforms developed to localize transcripts and proteins, imaging tools for visualization of metabolite distributions in plant tissues are less well developed and lack versatility. This hampers our understanding of plant metabolism and dynamics. In this study, we demonstrate that desorption electrospray ionization mass spectrometry imaging (DESI-MSI) of tissue imprints on porous Teflon may be used to accurately image the distribution of even labile plant metabolites such as hydroxynitrile glucosides, which normally undergo enzymatic hydrolysis by specific β-glucosidases upon cell disruption. This fast and simple sample preparation resulted in no substantial differences in the distribution and ratios of all hydroxynitrile glucosides between leaves from wild-type Lotus japonicus and a β-glucosidase mutant plant that lacks the ability to hydrolyze certain hydroxynitrile glucosides. In wild-type, the enzymatic conversion of hydroxynitrile glucosides and the concomitant release of glucose were easily visualized when a restricted area of the leaf tissue was damaged prior to sample preparation. The gene encoding the first enzyme in hydroxynitrile glucoside biosynthesis in L. japonicus leaves, CYP79D3, was found to be highly expressed during the early stages of leaf development, and the hydroxynitrile glucoside distribution in mature leaves reflected this early expression pattern. The utility of direct DESI-MSI of plant tissue was demonstrated using cryo-sections of cassava (Manihot esculenta) tubers. The hydroxynitrile glucoside levels were highest in the outer cell layers, as verified by LC-MS analyses. The unexpected discovery of a hydroxynitrile-derived di-glycoside shows the potential of DESI-MSI to discover and guide investigations into new metabolic routes.

  15. High-throughput proteomics using matrix-assisted laser desorption/ ionization mass spectrometry.

    PubMed

    Cramer, Rainer; Gobom, Johan; Nordhoff, Eckhard

    2005-06-01

    It has become evident that the mystery of life will not be deciphered just by decoding its blueprint, the genetic code. In the life and biomedical sciences, research efforts are now shifting from pure gene analysis to the analysis of all biomolecules involved in the machinery of life. One area of these postgenomic research fields is proteomics. Although proteomics, which basically encompasses the analysis of proteins, is not a new concept, it is far from being a research field that can rely on routine and large-scale analyses. At the time the term proteomics was coined, a gold-rush mentality was created, promising vast and quick riches (i.e., solutions to the immensely complex questions of life and disease). Predictably, the reality has been quite different. The complexity of proteomes and the wide variations in the abundances and chemical properties of their constituents has rendered the use of systematic analytical approaches only partially successful, and biologically meaningful results have been slow to arrive. However, to learn more about how cells and, hence, life works, it is essential to understand the proteins and their complex interactions in their native environment. This is why proteomics will be an important part of the biomedical sciences for the foreseeable future. Therefore, any advances in providing the tools that make protein analysis a more routine and large-scale business, ideally using automated and rapid analytical procedures, are highly sought after. This review will provide some basics, thoughts and ideas on the exploitation of matrix-assisted laser desorption/ ionization in biological mass spectrometry - one of the most commonly used analytical tools in proteomics - for high-throughput analyses. PMID:16000086

  16. Chemical Analysis of Complex Organic Mixtures Using Reactive Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Laskin, Julia; Eckert, Peter A.; Roach, Patrick J.; Heath, Brandi S.; Nizkorodov, Sergey A.; Laskin, Alexander

    2012-08-21

    Reactive nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was utilized for the analysis of secondary organic aerosol produced through ozonolysis of limonene (LSOA). Previous studies showed that LSOA constituents are multifunctional compounds containing aldehyde and ketone groups. In this study, we used the selectivity of the Girard T (GT) reagent towards carbonyl compounds to examine the utility of reactive nano-DESI for the analysis of complex organic mixtures. In these experiments, 1-100 {micro}M GT solution was used as a working solvent for reactive nano-DESI analysis. Abundant products of a single addition of GT to LSOA constituents were observed at GT concentrations in excess of 10 {micro}M. We found that LSOA compounds with 18-20 carbon atoms (dimers) and 27-30 carbon atoms (trimers) react with GT through a simple addition reaction resulting in formation of the carbinolamine derivative. In contrast, reactions of GT with monomeric species result in formation of both the carbinolamine and the hydrazone derivatives. In addition, several monomers did not react with GT on the timescale of our experiment. These molecules were characterized by relatively high values of the double bond equivalent (DBE) and low oxygen content. Furthermore, because addition of a charged GT tag to a neutral molecule eliminates the discrimination against the low proton affinity compounds in the ionization process, reactive nano-DESI analysis enables quantification of individual compounds in the complex mixture. For example, we were able to estimate for the first time the amounts of dimers and trimers in the LSOA mixture. Specifically, we found that the most abundant LSOA dimer was detected at ca. 0.5 pg level and the total amount of dimers and trimers in the analyzed sample was just around 11 pg. Our results indicate that reactive nano-DESI is a valuable approach for examining the presence of specific functional groups and

  17. Chemical analysis of complex organic mixtures using reactive nanospray desorption electrospray ionization mass spectrometry.

    PubMed

    Laskin, Julia; Eckert, Peter A; Roach, Patrick J; Heath, Brandi S; Nizkorodov, Sergey A; Laskin, Alexander

    2012-08-21

    Reactive nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was utilized for the analysis of secondary organic aerosol produced through ozonolysis of limonene (LSOA). Previous studies have shown that LSOA constituents are multifunctional compounds containing at least one aldehyde or ketone groups. In this study, we used the selectivity of the Girard's reagent T (GT) toward carbonyl compounds to examine the utility of reactive nano-DESI for the analysis of complex organic mixtures. In these experiments, 1-100 μM GT solutions were used as the working solvents for reactive nano-DESI analysis. Abundant products from the single addition of GT to LSOA constituents were observed at GT concentrations in excess of 10 μM. We found that LSOA dimeric and trimeric compounds react with GT through a simple addition reaction resulting in formation of the carbinolamine derivative. In contrast, reactions of GT with monomeric species result in the formation of both the carbinolamine and the hydrazone derivatives. In addition, several monomers did not react with GT on the time scale of our experiment. These molecules were characterized by relatively high values of the double bond equivalent and low oxygen content. Furthermore, because addition of a charged GT tag to a neutral molecule eliminates the discrimination against the low proton affinity compounds in the ionization process, reactive nano-DESI analysis enables quantification of individual compounds in the complex mixture. For example, we were able to estimate for the first time the amounts of dimers and trimers in the LSOA mixture. Specifically, we found that the most abundant LSOA dimer was detected at the ~0.5 pg level and the total amount of dimers and trimers in the analyzed sample was ~11 pg. Our results indicate that reactive nano-DESI is a valuable approach for examining the presence of specific functional groups and for the quantification of compounds possessing

  18. An investigation of liquid secondary ion and laser desorption mass spectroscopy for the analysis of planar chromatograms

    SciTech Connect

    Dunphy, J.C.

    1990-11-01

    In the work described in this dissertation, interfaces between two mass spectrometric methods, liquid secondary ion mass spectrometry (LSIMS) and laser desorption/ionization Fourier transform mass spectrometry (LD/FTMS), and thin-layer chromatography (TLC) and slab gel electrophoresis were developed for bioanalytical applications. In an investigation of direct LSIMS for TLC analysis (TLC/LSIMS), mass spectra of bile acids and bile salts were characterized directly from high-performance TLC plates. The scanning ability of the LSIMS instrument was used to generate spatial profiles of the characteristic bile acid ions in the mass spectra. A procedure for the analysis of bile salts in dog bile was developed involving an extraction step, followed by TLC separation and direct TLC/LSIMS detection and semi-quantitation. For peptides, an experiment called selected-sequence monitoring'' was developed to locate target peptides related in structure in complex mixtures developed on TLC plates. Ions characteristic of the bradykinin and enkephalin peptides were used to generate spatial profiles of members of those peptide families on TLC plates. Using a Fourier transform mass spectrometer (FTMS), a fundamental investigation was conducted into the factors affecting the quality of analytical data obtained using direct laser desorption/ionization to produce mass spectra from TLC plates.

  19. Chemical analysis of diesel engine nanoparticles using a nano-DMA/thermal desorption particle beam mass spectrometer.

    PubMed

    Tobias, H J; Beving, D E; Ziemann, P J; Sakurai, H; Zuk, M; McMurry, P H; Zarling, D; Waytulonis, R; Kittelson, D B

    2001-06-01

    Diesel engines are known to emit high number concentrations of nanoparticles (diameter < 50 nm), but the physical and chemical mechanisms by which they form are not understood. Information on chemical composition is lacking because the small size, low mass concentration, and potential for contamination of samples obtained by standard techniques make nanoparticles difficult to analyze. A nano-differential mobility analyzer was used to size-select nanoparticles (mass median diameter approximately 25-60 nm) from diesel engine exhaust for subsequent chemical analysis by thermal desorption particle beam mass spectrometry. Mass spectra were used to identify and quantify nanoparticle components, and compound molecular weights and vapor pressures were estimated from calibrated desorption temperatures. Branched alkanes and alkyl-substituted cycloalkanes from unburned fuel and/or lubricating oil appear to contribute most of the diesel nanoparticle mass. The volatility of the organic fraction of the aerosol increases as the engine load decreases and as particle size increases. Sulfuric acid was also detected at estimated concentrations of a few percent of the total nanoparticle mass. The results are consistent with a mechanism of nanoparticle formation involving nucleation of sulfuric acid and water, followed by particle growth by condensation of organic species.

  20. Thermal desorption-gas chromatography-mass spectrometry method to determine phthalate and organophosphate esters from air samples.

    PubMed

    Aragón, M; Borrull, F; Marcé, R M

    2013-08-16

    A method based on thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) has been developed to determine four organophosphate esters, seven phthalate esters, and bis(2-ethylhexyl) adipate in the gas phase from harbour and urban air samples. The method involves the sampling of 1.5L of air in a Tenax TA sorbent tube followed by thermal desorption (using a Tenax TA cryogenic trap) coupled to gas chromatography-mass spectrometry. The repeatability of the method expressed as %RSD (n=3) is less than 15% and the MQLs are between 0.007μgm(-3) (DMP, TBP, BBP, TPP and DnOP) and 6.7μgm(-3) (DEHP). The method was successfully applied in two areas (urban and harbour) testing two and three points in each one, respectively. Some of these compounds were found in both urban and harbour samples. Di-(2-ethylhexyl)phthalate was the most abundant compound found in both areas at concentration levels between 6.7μgm(-3) and 136.4μgm(-3). This study demonstrates that thermal desorption is an efficient method for the determination of these semi-volatile compounds in the gas phase fraction of air samples.

  1. Direct analysis of anabolic steroids in urine using Leidenfrost phenomenon assisted thermal desorption-dielectric barrier discharge ionization mass spectrometry.

    PubMed

    Saha, Subhrakanti; Mandal, Mridul Kanti; Nonami, Hiroshi; Hiraoka, Kenzo

    2014-08-11

    Rapid detection of trace level anabolic steroids in urine is highly desirable to monitor the consumption of performance enhancing anabolic steroids by athletes. The present article describes a novel strategy for identifying the trace anabolic steroids in urine using Leidenfrost phenomenon assisted thermal desorption (LPTD) coupled to dielectric barrier discharge (DBD) ionization mass spectrometry. Using this method the steroid molecules are enriched within a liquid droplet during the thermal desorption process and desorbed all-together at the last moment of droplet evaporation in a short time domain. The desorbed molecules were ionized using a dielectric barrier discharge ion-source in front of the mass spectrometer inlet at open atmosphere. This process facilitates the sensitivity enhancement with several orders of magnitude compared to the thermal desorption at a lower temperature. The limits of detection (LODs) of various steroid molecules were found to be in the range of 0.05-0.1 ng mL(-1) for standard solutions and around two orders of magnitude higher for synthetic urine samples. The detection limits of urinary anabolic steroids could be lowered by using a simple and rapid dichloromethane extraction technique. The analytical figures of merit of this technique were evaluated at open atmosphere using suitable internal standards. The technique is simple and rapid for high sensitivity and high throughput screening of anabolic steroids in urine.

  2. Jarosite as a Storage Mineral for Small Organic Molecules: Investigations of Natural Samples Using an 'In Situ' Laser Desorption Fourier Transform Mass Spectrometry Technique

    NASA Astrophysics Data System (ADS)

    Kotler, J. M.; Hinman, N. W.; Yan, B.; Stoner, D. L.; Scott, J. R.

    2007-03-01

    The use of laser desorption Fourier transform mass spectrometry has revealed the presence of organic matter in several jarosite samples from various locations worldwide including jarosite precipitated in the lab by acidothiobacillus ferroxidans.

  3. Automated ambient desorption-ionization platform for surface imaging integrated with a commercial Fourier transform ion cyclotron resonance mass spectrometer.

    PubMed

    Pól, Jaroslav; Vidová, Veronika; Kruppa, Gary; Kobliha, Václav; Novák, Petr; Lemr, Karel; Kotiaho, Tapio; Kostiainen, Risto; Havlícek, Vladimír; Volný, Michael

    2009-10-15

    A fully automated atmospheric pressure ionization platform has been built and coupled with a commercial high-resolution Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS) instrument. The outstanding performance of this instrument allowed screening on the basis of exact masses in imaging mode. The main novel aspect was in the integration of the atmospheric pressure ionization imaging into the current software for matrix-assisted laser desorption ionization (MALDI) imaging, which allows the user of this commercial dual-source mass spectrometer to perform MALDI-MS and different ambient MS imaging from the same user interface and to utilize the same software tools. Desorption electrospray ionization (DESI) and desorption atmospheric pressure photoionization (DAPPI) were chosen to test the ambient surface imaging capabilities of this new ionization platform. Results of DESI imaging experiments performed on brain tissue sections are in agreement with previous MS imaging reports obtained by DESI imaging, but due to the high resolution and mass accuracy of the FTICR instrument it was possible to resolve several ions at the same nominal mass in the DESI-MS spectra of brain tissue. These isobaric interferences at low resolution are due to the overlap of ions from different lipid classes with different biological relevance. It was demonstrated that with the use of high-resolution MS fast imaging screening of lipids can be achieved without any preseparation steps. DAPPI, which is a relatively new and less developed ambient ionization technique compared to DESI, was used in imaging mode for the first time ever. It showed promise in imaging of phytocompounds from plant leaves, and selective ionization of a sterol lipid was achieved by DAPPI from a brain tissue sample.

  4. Black phosphorus-assisted laser desorption ionization mass spectrometry for the determination of low-molecular-weight compounds in biofluids.

    PubMed

    He, Xiao-Mei; Ding, Jun; Yu, Lei; Hussain, Dilshad; Feng, Yu-Qi

    2016-09-01

    Quantitative analysis of small molecules by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been a challenging task due to matrix-derived interferences in low m/z region and poor reproducibility of MS signal response. In this study, we developed an approach by applying black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix for the quantitative analysis of small molecules for the first time. Black phosphorus-assisted laser desorption/ionization mass spectrometry (BP/ALDI-MS) showed clear background and exhibited superior detection sensitivity toward quaternary ammonium compounds compared to carbon-based materials. By combining stable isotope labeling (SIL) strategy with BP/ALDI-MS (SIL-BP/ALDI-MS), a variety of analytes labeled with quaternary ammonium group were sensitively detected. Moreover, the isotope-labeled forms of analytes also served as internal standards, which broadened the analyte coverage of BP/ALDI-MS and improved the reproducibility of MS signals. Based on these advantages, a reliable method for quantitative analysis of aldehydes from complex biological samples (saliva, urine, and serum) was successfully established. Good linearities were obtained for five aldehydes in the range of 0.1-20.0 μM with correlation coefficients (R (2)) larger than 0.9928. The LODs were found to be 20 to 100 nM. Reproducibility of the method was obtained with intra-day and inter-day relative standard deviations (RSDs) less than 10.4 %, and the recoveries in saliva samples ranged from 91.4 to 117.1 %. Taken together, the proposed SIL-BP/ALDI-MS strategy has proved to be a reliable tool for quantitative analysis of aldehydes from complex samples. Graphical Abstract An approach for the determination of small molecules was developed by using black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix. PMID:27382971

  5. Black phosphorus-assisted laser desorption ionization mass spectrometry for the determination of low-molecular-weight compounds in biofluids.

    PubMed

    He, Xiao-Mei; Ding, Jun; Yu, Lei; Hussain, Dilshad; Feng, Yu-Qi

    2016-09-01

    Quantitative analysis of small molecules by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been a challenging task due to matrix-derived interferences in low m/z region and poor reproducibility of MS signal response. In this study, we developed an approach by applying black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix for the quantitative analysis of small molecules for the first time. Black phosphorus-assisted laser desorption/ionization mass spectrometry (BP/ALDI-MS) showed clear background and exhibited superior detection sensitivity toward quaternary ammonium compounds compared to carbon-based materials. By combining stable isotope labeling (SIL) strategy with BP/ALDI-MS (SIL-BP/ALDI-MS), a variety of analytes labeled with quaternary ammonium group were sensitively detected. Moreover, the isotope-labeled forms of analytes also served as internal standards, which broadened the analyte coverage of BP/ALDI-MS and improved the reproducibility of MS signals. Based on these advantages, a reliable method for quantitative analysis of aldehydes from complex biological samples (saliva, urine, and serum) was successfully established. Good linearities were obtained for five aldehydes in the range of 0.1-20.0 μM with correlation coefficients (R (2)) larger than 0.9928. The LODs were found to be 20 to 100 nM. Reproducibility of the method was obtained with intra-day and inter-day relative standard deviations (RSDs) less than 10.4 %, and the recoveries in saliva samples ranged from 91.4 to 117.1 %. Taken together, the proposed SIL-BP/ALDI-MS strategy has proved to be a reliable tool for quantitative analysis of aldehydes from complex samples. Graphical Abstract An approach for the determination of small molecules was developed by using black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix.

  6. Mass spectrometric imaging and laser desorption ionization (LDI) with ice as a matrix using femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Berry, Jamal Ihsan

    The desorption of biomolecules from frozen aqueous solutions on metal substrates with femtosecond laser pulses is presented for the first time. Unlike previous studies using nanosecond pulses, this approach produces high quality mass spectra of biomolecules repeatedly and reproducibly. This novel technique allows analysis of biomolecules directly from their native frozen environments. The motivation for this technique stems from molecular dynamics computer simulations comparing nanosecond and picosecond heating of water overlayers frozen on Au substrates which demonstrate large water cluster formation and ejection upon substrate heating within ultrashort timescales. As the frozen aqueous matrix and analyte molecules are transparent at the wavelengths used, the laser energy is primarily absorbed by the substrate, causing rapid heating and explosive boiling of the ice overlayer, followed by the ejection of ice clusters and the entrained analyte molecule. Spectral characteristics at a relatively high fluence of 10 J/cm 2 reveal the presence of large molecular weight metal clusters when a gold substrate is employed, with smaller cluster species observed from frozen aqueous solutions on Ag, Cu, and Pb substrates. The presence of the metal clusters is indicative of an evaporative cooling mechanism which stabiles cluster ion formation and the ejection of biomolecules from frozen aqueous solutions. Solvation is necessary as the presence of metal clusters and biomolecular ion signals are not observed from bare metal substrates in absence of the frozen overlayer. The potential for mass spectrometric imaging with femtosecond LDI of frozen samples is also presented. The initial results for the characterization of peptides and peptoids linked to combinatorial beads frozen in ice and the assay of frozen brain tissue from the serotonin transporter gene knockout mouse via LDI imaging are discussed. Images of very good quality and resolution are obtained with 400 nm, 200 fs pulses

  7. Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry for the Discrimination of Food-Borne Microorganisms

    PubMed Central

    Mazzeo, Maria Fiorella; Sorrentino, Alida; Gaita, Marcello; Cacace, Giuseppina; Di Stasio, Michele; Facchiano, Angelo; Comi, Giuseppe; Malorni, Antonio; Siciliano, Rosa Anna

    2006-01-01

    A methodology based on matrix-assisted laser desorption ionization-time of flight mass spectrometry of intact bacterial cells was used for rapid discrimination of 24 bacterial species, and detailed analyses to identify Escherichia coli O157:H7 were carried out. Highly specific mass spectrometric profiles of pathogenic and nonpathogenic bacteria that are well-known major food contaminants were obtained, uploaded in a specific database, and made available on the Web. In order to standardize the analytical protocol, several experimental, sample preparation, and mass spectrometry parameters that can affect the reproducibility and accuracy of data were evaluated. Our results confirm the conclusion that this strategy is a powerful tool for rapid and accurate identification of bacterial species and that mass spectrometric methodologies could play an essential role in polyphasic approaches to the identification of pathogenic bacteria. PMID:16461665

  8. Desorption Electrospray Ionization (DESI) Mass Spectrometric Imaging of the Distribution of Rohitukine in the Seedling of Dysoxylum binectariferum Hook. F

    PubMed Central

    Mohana Kumara, Patel; Srimany, Amitava; Arunan, Suganya; Ravikanth, Gudasalamani; Uma Shaanker, Ramanan; Pradeep, Thalappil

    2016-01-01

    Ambient ionization mass spectrometric imaging of all parts of the seedling of Dysoxylum binectariferum Hook. f (Meliaceae) was performed to reconstruct the molecular distribution of rohitukine (Rh) and related compounds. The species accumulates Rh, a prominent chromone alkaloid, in its seeds, fruits, and stem bark. Rh possesses anti-inflammatory, anti-cancer, and immuno-modulatory properties. Desorption electrospray ionization mass spectrometry imaging (DESI MSI) and electrospray ionization (ESI) tandem mass spectrometry (MS/MS) analysis detected Rh as well as its glycosylated, acetylated, oxidized, and methoxylated analogues. Rh was predominantly distributed in the main roots, collar region of the stem, and young leaves. In the stem and roots, Rh was primarily restricted to the cortex region. The identities of the metabolites were assigned based on both the fragmentation patterns and exact mass analyses. We discuss these results, with specific reference to the possible pathways of Rh biosynthesis and translocation during seedling development in D. binectariferum. PMID:27362422

  9. Laser desorption/ionization mass spectrometry for direct profiling and imaging of small molecules from raw biological materials

    SciTech Connect

    Cha, Sangwon

    2008-01-01

    Matrix-assisted laser desorption/ionization(MALDI) mass spectrometry(MS) has been widely used for analysis of biological molecules, especially macromolecules such as proteins. However, MALDI MS has a problem in small molecule (less than 1 kDa) analysis because of the signal saturation by organic matrixes in the low mass region. In imaging MS (IMS), inhomogeneous surface formation due to the co-crystallization process by organic MALDI matrixes limits the spatial resolution of the mass spectral image. Therefore, to make laser desorption/ionization (LDI) MS more suitable for mass spectral profiling and imaging of small molecules directly from raw biological tissues, LDI MS protocols with various alternative assisting materials were developed and applied to many biological systems of interest. Colloidal graphite was used as a matrix for IMS of small molecules for the first time and methodologies for analyses of small metabolites in rat brain tissues, fruits, and plant tissues were developed. With rat brain tissues, the signal enhancement for cerebroside species by colloidal graphite was observed and images of cerebrosides were successfully generated by IMS. In addition, separation of isobaric lipid ions was performed by imaging tandem MS. Directly from Arabidopsis flowers, flavonoids were successfully profiled and heterogeneous distribution of flavonoids in petals was observed for the first time by graphite-assisted LDI(GALDI) IMS.

  10. Cellular Level Mass Spectrometry Imaging using Infrared Matrix Assisted Laser Desorption Electrospray Ionization (IR-MALDESI) by Oversampling

    PubMed Central

    Nazari, Milad; Muddiman, David C.

    2014-01-01

    Mass spectrometry imaging (MSI) allows for the direct and simultaneous analysis of the spatial distribution of molecular species from sample surfaces such as tissue sections. One of the goals of MSI is monitoring the distribution of compounds at the cellular resolution in order to gain insights about the biology that occurs at this spatial level. Infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) imaging of cervical tissue sections was performed using a spot-to-spot distance of 10 μm by utilizing the method of oversampling; where the target plate is moved by a distance that is less than the desorption radius of the laser. In addition to high spatial resolution, high mass accuracy (± 1 ppm) and high mass resolving power (140,000 at m/z=200) was achieved by coupling the IR-MALDESI imaging source to a hybrid quadrupole Orbitrap mass spectrometer. Ion maps of cholesterol in tissues were generated from voxels containing <1 cell, on average. Additionally, the challenges of imaging at the cellular level in terms of loss of sensitivity and longer analysis time are discussed. PMID:25486925

  11. Evaluation of combined matrix-assisted laser desorption/ionization time-of-flight and matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry experiments for peptide mass fingerprinting analysis.

    PubMed

    da Silva, David; Wasselin, Thierry; Carré, Vincent; Chaimbault, Patrick; Bezdetnaya, Lina; Maunit, Benoît; Muller, Jean-François

    2011-07-15

    Peptide Mass Fingerprinting (PMF) is still of significant interest in proteomics because it allows a large number of complex samples to be rapidly screened and characterized. The main part of post-translational modifications is generally preserved. In some specific cases, PMF suffers from ambiguous or unsuccessful identification. In order to improve its reliability, a combined approach using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) and matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICRMS) was evaluated. The study was carried out on bovine serum albumin (BSA) digest. The influence of several important parameters (the matrix, the sample preparation method, the amount of the analyte) on the MOWSE score and the protein sequence coverage were evaluated to allow the identification of specific effects. A careful investigation of the sequence coverage obtained by each kind of experiment ensured the detection of specific peptides for each experimental condition. Results highlighted that DHB-FTICRMS and DHB- or CHCA-TOFMS are the most suited combinations of experimental conditions to achieve PMF analysis. The association (convolution) of the data obtained by each of these techniques ensured a significant increase in the MOWSE score and the protein sequence coverage.

  12. Filtration efficiency validation of glass wool during thermal desorption-gas chromatography-mass spectrometer analysis of fine atmospheric particles.

    PubMed

    Hao, Liang; Wu, Dapeng; Ding, Kun; Meng, Hu; Yan, Xiaohui; Guan, Yafeng

    2015-02-01

    Thermal desorption-gas chromatography-mass spectrometer (TD-GC-MS) technique has been widely used for analysis of semi-violate organic compounds on atmospheric aerosol. To prevent GC column from being damaged by fine solid particles during thermal desorption process, glass wool as filter mat is indispensible. However, the filtration efficiency has never been validated. In this paper, the most penetrating particle size and the minimum packing thickness of glass wool were calculated based on classical filtration theory. According to the calculation results, packing parameters of glass wool were optimized experimentally using silica particles. It is demonstrated that glass wool with a packing thickness of 30 mm, solidity of 0.039 can effectively block these fine solid particles from penetrating at normal thermal desorption conditions (T=300°C, u=0.4-4 cm/s). Finally, the filtration efficiency of glass wool was further confirmed with real PM2.5 samples. Under the validated filtration condition, TD-GC-MS was applied for the analysis of non-polar organic compounds on real PM2.5 samples, and very good results were obtained.

  13. Using electrospray laser desorption ionization mass spectrometry to rapidly examine the integrity of proteins stored in various solutions.

    PubMed

    Cho, Yi-Tzu; Huang, Min-Zong; Wu, Sih-You; Hou, Ming-Feng; Li, Jianjun; Shiea, Jentaie

    2014-01-01

    Electrospray laser desorption ionization mass spectrometry (ELDI/MS) allows the rapid desorption and ionization of proteins from solutions under ambient conditions. In this study, we have demonstrated the use of ELDI/MS to efficiently examine the integrity of the proteins stored in various solutions before they were further used for other biochemical tests. The protein standards were prepared in the solutions containing buffers, organic salts, inorganic salts, strong acid, strong base, and organic solvents, respectively, to simulate those collected from solvent extraction, filtration, dialysis, or chromatographic separation. Other than the deposit of a drop of the sample solution on the metallic sample plate in an ELDI source, no additional sample pretreatment is needed. The sample drop was then irradiated with a pulsed laser; this led to desorption of the analyte molecules, which subsequently entered the ESI plume to undergo post-ionization. Because adjustment of the composition of the sample solution is unnecessary, this technique appears to be useful for rapidly evaluating the integrity of proteins after storage or prior to further biochemical treatment. In addition, when using acid-free and low-organic-solvent ESI solutions for ELDI/MS analysis, the native conformations of the proteins in solution could be detected.

  14. Mycobacterium abscessus Complex Identification with Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry

    PubMed Central

    Panagea, Theofano; Pincus, David H.; Grogono, Dorothy; Jones, Melissa; Bryant, Josephine; Parkhill, Julian; Floto, R. Andres

    2015-01-01

    We determined that the Vitek MS Plus matrix-assisted laser desorption ionization–time of flight mass spectrometry using research-use-only (RUO) v.4.12 and in vitro-diagnostic (IVD) v.3.0 databases accurately identified 41 Mycobacterium abscessus subsp. abscessus and 13 M. abscessus subsp. massiliense isolates identified by whole-genome sequencing to the species but not the subspecies level, from Middlebrook 7H11 and Burkholderia cepacia selective agars. Peak analysis revealed three peaks potentially able to differentiate between subspecies. PMID:25948607

  15. Mycobacterium abscessus Complex Identification with Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry.

    PubMed

    Panagea, Theofano; Pincus, David H; Grogono, Dorothy; Jones, Melissa; Bryant, Josephine; Parkhill, Julian; Floto, R Andres; Gilligan, Peter

    2015-07-01

    We determined that the Vitek MS Plus matrix-assisted laser desorption ionization-time of flight mass spectrometry using research-use-only (RUO) v.4.12 and in vitro-diagnostic (IVD) v.3.0 databases accurately identified 41 Mycobacterium abscessus subsp. abscessus and 13 M. abscessus subsp. massiliense isolates identified by whole-genome sequencing to the species but not the subspecies level, from Middlebrook 7H11 and Burkholderia cepacia selective agars. Peak analysis revealed three peaks potentially able to differentiate between subspecies. PMID:25948607

  16. Authenticity assessment of beef origin by principal component analysis of matrix-assisted laser desorption/ionization mass spectrometric data.

    PubMed

    Zaima, Nobuhiro; Goto-Inoue, Naoko; Hayasaka, Takahiro; Enomoto, Hirofumi; Setou, Mitsutoshi

    2011-06-01

    It has become necessary to assess the authenticity of beef origin because of concerns regarding human health hazards. In this study, we used a metabolomic approach involving matrix-assisted laser desorption/ionization imaging mass spectrometry to assess the authenticity of beef origin. Highly accurate data were obtained for samples of extracted lipids from beef of different origin; the samples were grouped according to their origin. The analysis of extracted lipids in this study ended within 10 min, suggesting this approach can be used as a simple authenticity assessment before a definitive identification by isotope analysis.

  17. Current status of matrix-assisted laser desorption ionisation-time of flight mass spectrometry in the clinical microbiology laboratory.

    PubMed

    Kok, Jen; Chen, Sharon C A; Dwyer, Dominic E; Iredell, Jonathan R

    2013-01-01

    The integration of matrix-assisted laser desorption ionisation-time of flight mass spectrometry (MALDI-TOF MS) into many clinical microbiology laboratories has revolutionised routine pathogen identification. MALDI-TOF MS complements and has good potential to replace existing phenotypic identification methods. Results are available in a more clinically relevant timeframe, particularly in bacteraemic septic shock. Novel applications include strain typing and the detection of antimicrobial resistance, but these are not widely used. This review discusses the technical aspects, current applications, and limitations of MALDI-TOF MS.

  18. Matrix-assisted laser desorption mass spectrometry of gas-phase peptide-metal complexes

    NASA Astrophysics Data System (ADS)

    Hortal, Ana R.; Hurtado, Paola; Martínez-Haya, Bruno

    2008-12-01

    Cation attachment to a model peptide has been investigated in matrix-assisted laser desorption experiments. Angiotensin I (Asp-Arg-Val-Tyr-Ile-His-Pro-Phe-His-Leu) is chosen as a system for study, and Cu2+ and K+ salts are used as cationizing agents. Three fundamentally different types of samples are investigated: (1) a crystalline sample of Ang I, metal salt and MALDI matrix, prepared with the conventional dried droplet method; (2) a solvent-free fine powder mixture of the same three compounds, and (3) a solution of the angiotensin and the metal salt in an ionic liquid matrix (a molten organic salt that acts as a MALDI active solvent). Effective protonation and cationization of the peptide are achieved with the three methods. The transition metal systematically provides more efficient cationization than the alkali metal. At sufficiently high concentration of the salt, the attachment of up to four copper cations to the angiotensin is observed in the MALDI spectrum. In contrast, only one K+ cation is efficiently bound to the peptide. For a given salt concentration, the highest degree of cationization is obtained in the laser desorption from the ionic liquid matrix. This is attributed to the efficient transfer of free metal cations to the desorption plume, where the complexation takes place.

  19. Detection of trace organics in Mars analog samples containing perchlorate by laser desorption/ionization mass spectrometry.

    PubMed

    Li, Xiang; Danell, Ryan M; Brinckerhoff, William B; Pinnick, Veronica T; van Amerom, Friso; Arevalo, Ricardo D; Getty, Stephanie A; Mahaffy, Paul R; Steininger, Harald; Goesmann, Fred

    2015-02-01

    Evidence from recent Mars missions indicates the presence of perchlorate salts up to 1 wt % level in the near-surface materials. Mixed perchlorates and other oxychlorine species may complicate the detection of organic molecules in bulk martian samples when using pyrolysis techniques. To address this analytical challenge, we report here results of laboratory measurements with laser desorption mass spectrometry, including analyses performed on both commercial and Mars Organic Molecule Analyzer (MOMA) breadboard instruments. We demonstrate that the detection of nonvolatile organics in selected spiked mineral-matrix materials by laser desorption/ionization (LDI) mass spectrometry is not inhibited by the presence of up to 1 wt % perchlorate salt. The organics in the sample are not significantly degraded or combusted in the LDI process, and the parent molecular ion is retained in the mass spectrum. The LDI technique provides distinct potential benefits for the detection of organics in situ on the martian surface and has the potential to aid in the search for signs of life on Mars.

  20. Direct Visualization of Neurotransmitters in Rat Brain Slices by Desorption Electrospray Ionization Mass Spectrometry Imaging (DESI - MS)

    NASA Astrophysics Data System (ADS)

    Fernandes, Anna Maria A. P.; Vendramini, Pedro H.; Galaverna, Renan; Schwab, Nicolas V.; Alberici, Luciane C.; Augusti, Rodinei; Castilho, Roger F.; Eberlin, Marcos N.

    2016-10-01

    Mass spectrometry imaging (MSI) of neurotransmitters has so far been mainly performed by matrix-assisted laser desorption/ionization (MALDI) where derivatization reagents, deuterated matrix and/or high resolution, or tandem MS have been applied to circumvent problems with interfering ion peaks from matrix and from isobaric species. We herein describe the application of desorption electrospray ionization mass spectrometry imaging (DESI)-MSI in rat brain coronal and sagittal slices for direct spatial monitoring of neurotransmitters and choline with no need of derivatization reagents and/or deuterated materials. The amino acids γ-aminobutyric (GABA), glutamate, aspartate, serine, as well as acetylcholine, dopamine, and choline were successfully imaged using a commercial DESI source coupled to a hybrid quadrupole-Orbitrap mass spectrometer. The spatial distribution of the analyzed compounds in different brain regions was determined. We conclude that the ambient matrix-free DESI-MSI is suitable for neurotransmitter imaging and could be applied in studies that involve evaluation of imbalances in neurotransmitters levels.

  1. Detection of trace organics in Mars analog samples containing perchlorate by laser desorption/ionization mass spectrometry.

    PubMed

    Li, Xiang; Danell, Ryan M; Brinckerhoff, William B; Pinnick, Veronica T; van Amerom, Friso; Arevalo, Ricardo D; Getty, Stephanie A; Mahaffy, Paul R; Steininger, Harald; Goesmann, Fred

    2015-02-01

    Evidence from recent Mars missions indicates the presence of perchlorate salts up to 1 wt % level in the near-surface materials. Mixed perchlorates and other oxychlorine species may complicate the detection of organic molecules in bulk martian samples when using pyrolysis techniques. To address this analytical challenge, we report here results of laboratory measurements with laser desorption mass spectrometry, including analyses performed on both commercial and Mars Organic Molecule Analyzer (MOMA) breadboard instruments. We demonstrate that the detection of nonvolatile organics in selected spiked mineral-matrix materials by laser desorption/ionization (LDI) mass spectrometry is not inhibited by the presence of up to 1 wt % perchlorate salt. The organics in the sample are not significantly degraded or combusted in the LDI process, and the parent molecular ion is retained in the mass spectrum. The LDI technique provides distinct potential benefits for the detection of organics in situ on the martian surface and has the potential to aid in the search for signs of life on Mars. PMID:25622133

  2. Structural characterization of phospholipids by matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Marto, J A; White, F M; Seldomridge, S; Marshall, A G

    1995-11-01

    Matrix-assisted laser desorption/ionization (MALDI) Fourier transform ion cyclotron resonance mass spectrometry provides for structural analysis of the principal biological phospholipids: glycerophosphatidylcholine, -ethanolamine, -serine, and -inositol. Both positive and negative molecular or quasimolecular ions are generated in high abundance. Isolated molecular ions may be collisionally activated in the source side of a dual trap mass analyzer, yielding fragments serving to identify the polar head group (positive ion mode) and fatty acid side chains (negative ion mode). Azimuthal quadrupolar excitation following collisionally activated dissociation refocuses productions close to the solenoid axis; subsequent transfer of product ions to the analyzer ion trap allows for high-resolution mass analysis. Cyro-cooling of the sample probe with liquid nitrogen greatly reduces matrix adduction encountered in the negative ion mode.

  3. Surface analysis using a new plasma assisted desorption/ionisation source for mass spectrometry in ambient air

    NASA Astrophysics Data System (ADS)

    Bowfield, A.; Barrett, D. A.; Alexander, M. R.; Ortori, C. A.; Rutten, F. M.; Salter, T. L.; Gilmore, I. S.; Bradley, J. W.

    2012-06-01

    The authors report on a modified micro-plasma assisted desorption/ionisation (PADI) device which creates plasma through the breakdown of ambient air rather than utilising an independent noble gas flow. This new micro-PADI device is used as an ion source for ambient mass spectrometry to analyse species released from the surfaces of polytetrafluoroethylene, and generic ibuprofen and paracetamol tablets through remote activation of the surface by the plasma. The mass spectra from these surfaces compare favourably to those produced by a PADI device constructed using an earlier design and confirm that the new ion source is an effective device which can be used to achieve ambient mass spectrometry with improved spatial resolution.

  4. Direct detection of pharmaceuticals and personal care products from aqueous samples with thermally-assisted desorption electrospray ionization mass spectrometry.

    PubMed

    Campbell, Ian S; Ton, Alain T; Mulligan, Christopher C

    2011-07-01

    An ambient mass spectrometric method based on desorption electrospray ionization (DESI) has been developed to allow rapid, direct analysis of contaminated water samples, and the technique was evaluated through analysis of a wide array of pharmaceutical and personal care product (PPCP) contaminants. Incorporating direct infusion of aqueous sample and thermal assistance into the source design has allowed low ppt detection limits for the target analytes in drinking water matrices. With this methodology, mass spectral information can be collected in less than 1 min, consuming ~100 μL of total sample. Quantitative ability was also demonstrated without the use of an internal standard, yielding decent linearity and reproducibility. Initial results suggest that this source configuration is resistant to carryover effects and robust towards multi-component samples. The rapid, continuous analysis afforded by this method offers advantages in terms of sample analysis time and throughput over traditional hyphenated mass spectrometric techniques.

  5. Matrix-assisted laser desorption/ionisation mass spectrometry imaging and its development for plant protein imaging

    PubMed Central

    2011-01-01

    Matrix-Assisted Laser Desorption/Ionisation (MALDI) mass spectrometry imaging (MSI) uses the power of high mass resolution time of flight (ToF) mass spectrometry coupled to the raster of lasers shots across the cut surface of tissues to provide new insights into the spatial distribution of biomolecules within biological tissues. The history of this technique in animals and plants is considered and the potential for analysis of proteins by this technique in plants is discussed. Protein biomarker identification from MALDI-MSI is a challenge and a number of different approaches to address this bottleneck are discussed. The technical considerations needed for MALDI-MSI are reviewed and these are presented alongside examples from our own work and a protocol for MALDI-MSI of proteins in plant samples. PMID:21726462

  6. Discrimination between bacterial spore types using time-of-flight mass spectrometry and matrix-free infrared laser desorption and ionization.

    PubMed

    Ullom, J N; Frank, M; Gard, E E; Horn, J M; Labov, S E; Langry, K; Magnotta, F; Stanion, K A; Hack, C A; Benner, W H

    2001-05-15

    We demonstrate that molecular ions with mass-to-charge ratios (m/z) ranging from a few hundred to 19 050 can be desorbed from whole bacterial spores using infrared laser desorption and no chemical matrix. We have measured the mass of these ions using time-of-flight mass spectrometry and we observe that different ions are desorbed from spores of Bacillus cereus, Bacillus thuringiensis, Bacillus subtilis, and Bacillus niger. Our results raise the possibility of identifying microorganisms using mass spectrometry without conventional sample preparation techniques such as the addition of a matrix. We have measured the dependence of the ion yield from B. subtilis on desorption wavelength over the range 3.05-3.8 microm, and we observe the best results at 3.05 microm. We have also generated mass spectra from whole spores using 337-nm ultraviolet laser desorption, and we find that these spectra are inferior to spectra generated with infrared desorption. Since aerosol analysis is a natural application for matrix-free desorption, we have measured mass spectra from materials such as ragweed pollen and road dust that are likely to form a background to microbial aerosols. We find that these materials are readily differentiated from bacterial spores.

  7. Electrospun Nanofiber Mats as "Smart Surfaces" for Desorption Electrospray Ionization Mass Spectrometry (DESI MS)-Based Analysis and Imprint Imaging.

    PubMed

    Hemalatha, R G; Ganayee, Mohd Azhardin; Pradeep, T

    2016-06-01

    In this paper, desorption electrospray ionization mass spectrometry (DESI MS)-based molecular analysis and imprint imaging using electrospun nylon-6 nanofiber mats are demonstrated for various analytical contexts. Uniform mats of varying thicknesses composed of ∼200 nm diameter fibers were prepared using needleless electrospinning. Analytical applications requiring rapid understanding of the analytes in single drops, dyes, inks, and/or plant extracts incorporated directly into the nanofibers are discussed with illustrations. The possibility to imprint patterns made of printing inks, plant parts (such as petals, leaves, and slices of rhizomes), and fungal growth on fruits with their faithful reproductions on the nanofiber mats is illustrated with suitable examples. Metabolites were identified by tandem mass spectrometry data available in the literature and in databases. The results highlight the significance of electrospun nanofiber mats as smart surfaces to capture diverse classes of compounds for rapid detection or to imprint imaging under ambient conditions. Large surface area, appropriate chemical functionalities exposed, and easiness of desorption due to weaker interactions of the analyte species are the specific advantages of nanofibers for this application. PMID:27159150

  8. Solvent Separating Secondary Metabolites Directly from Biosynthetic Tissue for Surface-Assisted Laser Desorption Ionisation Mass Spectrometry

    PubMed Central

    Rudd, David; Benkendorff, Kirsten; Voelcker, Nicolas H.

    2015-01-01

    Marine bioactive metabolites are often heterogeneously expressed in tissues both spatially and over time. Therefore, traditional solvent extraction methods benefit from an understanding of the in situ sites of biosynthesis and storage to deal with heterogeneity and maximize yield. Recently, surface-assisted mass spectrometry (MS) methods namely nanostructure-assisted laser desorption ionisation (NALDI) and desorption ionisation on porous silicon (DIOS) surfaces have been developed to enable the direct detection of low molecular weight metabolites. Since direct tissue NALDI-MS or DIOS-MS produce complex spectra due to the wide variety of other metabolites and fragments present in the low mass range, we report here the use of “on surface” solvent separation directly from mollusc tissue onto nanostructured surfaces for MS analysis, as a mechanism for simplifying data annotation and detecting possible artefacts from compound delocalization during the preparative steps. Water, ethanol, chloroform and hexane selectively extracted a range of choline esters, brominated indoles and lipids from Dicathais orbita hypobranchial tissue imprints. These compounds could be quantified on the nanostructured surfaces by comparison to standard curves generated from the pure compounds. Surface-assisted MS could have broad utility for detecting a broad range of secondary metabolites in complex marine tissue samples. PMID:25786067

  9. Highly Reproducible Laser Beam Scanning Device for an Internal Source Laser Desorption Microprobe Fourier Transform Mass Spectrometer

    SciTech Connect

    Scott, Jill Rennee; Tremblay, Paul Leland

    2002-03-01

    Traditionally, mass spectrometry has relied on manipulating the sample target to provide scanning capabilities for laser desorption microprobes. This has been problematic for an internal source laser desorption Fourier transform mass spectrometer (LD-FTMS) because of the high magnetic field (7 Tesla) and geometric constraints of the superconducting magnet bore. To overcome these limitations, we have implemented a unique external laser scanning mechanism for an internal source LD-FTMS. This mechanism provides adjustable resolution enhancement so that the spatial resolution at the target is not limited to that of the stepper motors at the light source (~5 µm/step). The spatial resolution is now limited by the practical optical diffraction limit of the final focusing lens. The scanning mechanism employs a virtual source that is wavelength independent up to the final focusing lens, which can be controlled remotely to account for focal length dependence on wavelength. A binary index provides an automatic alignment feature. The virtual source is located ~9 ft from the sample; therefore, it is completely outside of the vacuum system and beyond the 50 G line of the fringing magnetic field. To eliminate reproducibility problems associated with vacuum pump vibrations, we have taken advantage of the magnetic field inherent to the FTMS to utilize Lenz's law for vibrational dampening. The LD-FTMS microprobe has exceptional reproducibility, which enables successive mapping sequences for depth-profiling studies.

  10. Highly reproducible laser beam scanning device for an internal source laser desorption microprobe Fourier transform mass spectrometer

    NASA Astrophysics Data System (ADS)

    Scott, Jill R.; Tremblay, Paul L.

    2002-03-01

    Traditionally, mass spectrometry has relied on manipulating the sample target to provide scanning capabilities for laser desorption microprobes. This has been problematic for an internal source laser desorption Fourier transform mass spectrometer (LD-FTMS) because of the high magnetic field (7 Tesla) and geometric constraints of the superconducting magnet bore. To overcome these limitations, we have implemented a unique external laser scanning mechanism for an internal source LD-FTMS. This mechanism provides adjustable resolution enhancement so that the spatial resolution at the target is not limited to that of the stepper motors at the light source (˜5 μm/step). The spatial resolution is now limited by the practical optical diffraction limit of the final focusing lens. The scanning mechanism employs a virtual source that is wavelength independent up to the final focusing lens, which can be controlled remotely to account for focal length dependence on wavelength. A binary index provides an automatic alignment feature. The virtual source is located ˜9 ft from the sample; therefore, it is completely outside of the vacuum system and beyond the 50 G line of the fringing magnetic field. To eliminate reproducibility problems associated with vacuum pump vibrations, we have taken advantage of the magnetic field inherent to the FTMS to utilize Lenz's law for vibrational dampening. The LD-FTMS microprobe has exceptional reproducibility, which enables successive mapping sequences for depth-profiling studies.

  11. Synergistic effect of graphene oxide/MWCNT films in laser desorption/ionization mass spectrometry of small molecules and tissue imaging.

    PubMed

    Kim, Young-Kwan; Na, Hee-Kyung; Kwack, Sul-Jin; Ryoo, Soo-Ryoon; Lee, Youngmi; Hong, Seunghee; Hong, Sungwoo; Jeong, Yong; Min, Dal-Hee

    2011-06-28

    Matrix-assisted laser desorption/ionization mass spectrometry has been considered an important tool for various biochemical analyses and proteomics research. Although addition of conventional matrix efficiently supports laser desorption/ionization of analytes with minimal fragmentation, it often results in high background interference and misinterpretation of the spatial distribution of biomolecules especially in low-mass regions. Here, we show design, systematic characterization, and application of graphene oxide/multiwalled carbon nanotube-based films fabricated on solid substrates as a new matrix-free laser desorption/ionization platform. We demonstrate that the graphene oxide/multiwalled carbon nanotube double layer provides many advantages as a laser desorption/ionization substrate, such as efficient desorption/ionization of analytes with minimum fragmentation, high salt tolerance, no sweet-spots for mass signal, excellent durability against mechanical and photoagitation and prolonged exposure to ambient conditions, and applicability to tissue imaging mass spectrometry. This platform will be widely used as an important tool for mass spectrometry-based biochemical analyses because of its outstanding performance, long-term stability, and cost effectiveness.

  12. Combined Chemical and Topographic Imaging at Atmospheric Pressure via Microprobe Laser Desorption/Ionization Mass Spectrometry-Atomic Force Microscopy

    SciTech Connect

    Bradshaw, James A; Ovchinnikova, Olga S; Meyer, Kent A; Goeringer, Doug

    2009-01-01

    The operational characteristics and imaging performance are described for a new instrument comprising an atomic force microscope (AFM) coupled with a pulsed laser and a linear ion trap mass spectrometer. The AFM operating mode is used to produce topographic surface images having nanometer-scale spatial and height resolution. Spatially resolved mass spectra of ions, produced from the same surface via microprobe-mode laser desorption/ionization at atmospheric pressure, are then used to create a 100 x 100 m chemical image. The effective spatial resolution of the image (~2 m) was constrained by the limit of detection (estimated to be 109 1010 ions) rather than by the diameter of the focused laser spot or the step size of the AFM sample stage. Thus, it is expected that improvements in imaging performance can be realized by implementation of post-ionization methods.

  13. Application of atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry for rapid identification of Neisseria species.

    PubMed

    Gudlavalleti, Seshu K; Sundaram, Appavu K; Razumovski, Jane; Doroshenko, Vladimir

    2008-07-01

    Atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry (AP-MALDI MS) was applied to develop a proteomics-based method to detect and identify Neisseria species. Heat-inactivated clinical isolate cell suspensions of Neisseria gonorrhoeae and strains belonging to five serogroups (A, B, C, W135, and Y) of Neisseria meningitidis were subjected to on-probe protein/peptide extraction and tryptic digestion followed by AP-MALDI tandem MS (MS/MS)-based proteomic analysis. Amino acid sequences derived from three protonated peptides with m/z values of 1743.8, 1894.8, and 1946.8 were identified by AP-MALDI MS/MS and MASCOT proteome database search analysis as belonging to neisserial acyl carrier protein, neisserial-conserved hypothetical protein, and neisserial putative DNA binding protein, respectively. These three peptide masses can thus be potential biomarkers for neisserial species identification by AP-MALDI MS.

  14. Functional wave time-lag focusing matrix-assisted laser desorption/ionization in a linear time-of-flight mass spectrometer: improved mass accuracy.

    PubMed

    Whittal, R M; Russon, L M; Weinberger, S R; Li, L

    1997-06-01

    A strength of matrix-assisted laser desorption/ionization (MALDI) mass spectrometry is its ability to analyze mixtures without separation. MALDI mass spectrometers capable of providing a linear mass calibration over a broad mass range should find wide use in these applications. This work addresses issues pertinent to mass measurement accuracy of a time-lag focusing MALDI time-of-flight instrument and presents a new approach to improving mass accuracy by using a functional wave extraction pulse, instead of a square wave, for time-lag focusing. A model is described of an ideal extraction pulse shape that provides constant total kinetic energy for all ions. If total kinetic energy is constant, then there is an exact linear correlation between ion mass and flight time raised to the second power. Using a descending wave extraction pulse, it is demonstrated that mass accuracy of better than 30 ppm using two internal calibrants and better than 70 ppm using external calibrants can be obtained over a 25 ku mass range. The practical aspects of an instrument needed to obtain consistent mass accuracy is discussed. It is found that ion flight time shows a small dependence upon laser flux; flight times increase slightly as the flux increases. But this dependence is much smaller than is observed in continuous-extraction MALDI.

  15. A SIMPLE AND RAPID MATRIX-ASSISTED LASER DESORPTION/IONIZATION TIME OF FLIGHT MASS SPECTROMETRY METHOD TO SCREEN FISH PLASMA SAMPLES FOR ESTROGEN-RESPONSIVE BIOMARKERS

    EPA Science Inventory

    In this study, we describe and evaluate the performance of a simple and rapid mass spectral method for screening fish plasma for estrogen-responsive biomarkers using matrix assisted laster desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS) couopled with a short...

  16. Detecting Biosignatures Associated with Minerals by Geomatrix-Assisted Laser Desorption/Ionization Fourier Transorm Mass Spectromety (GALDI-FTMS)

    SciTech Connect

    C. Doc Richardson; J. Michelle Kotler; Nancy W. Hinman; Timothy R. McJunkin; Jill R. Scott

    2008-07-01

    The ability to detect carbon signatures that can be linked to complex, possibly biogenic, organic molecules is imperative in research into the origin and distribution of life in our solar system particularly when used in conjunction with inorganic, mineralogical, and isotopic signatures that provide strong evidence for geochemical influences of living organisms on their environment. Ideally, the method used to detect these signatures must (i) accurately and automatically translate the organic and other information into usable forms, (ii) precisely distinguish such information from alternative compositions, (iii) operate with high spatial resolution coupled with precise location abilities, and (iv) require little to no sample preparation because of the potential for contamination. Geomatrix-assisted laser desorption/ionization (GALDI) in conjunction with a Fourier transform mass spectrometer (FTMS) has been used to determine the presence of bio/organic molecules (BOM) associated with different minerals and mineraloids including oxide, sulfate, carbonate, chloride, and silicate minerals. BOM is defined as an organic structure that can be produced by living organisms or derived from another organic compound made by living organisms (i.e., degradation product). GALDI requires no sample preparation because the mineral matrix assists desorption. Ultimately, however, the detectability of BOM is controlled by the desorption efficiency, ionization efficiency, and the specific experimental conditions. Results from experiments with combinations of known BOM and mineral standards indicated that the detectability of BOM increased with decreasing concentration, contrary to most analytical procedures. Results suggest that BOM when combined with certain minerals is more easily detected than when combined with other minerals. Such conclusions can guide selection of appropriate samples for sample return missions.

  17. A simple algorithm improves mass accuracy to 50-100 ppm for delayed extraction linear matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Hack, Christopher A; Benner, W Henry

    2002-01-01

    A simple mathematical technique for improving mass calibration accuracy of linear delayed extraction matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (DE MALDI-TOFMS) spectra is presented. The method involves fitting a parabola to a plot of Delta(m) vs. mass data where Delta(m) is the difference between the theoretical mass of calibrants and the mass obtained from a linear relationship between the square root of m/z and ion time of flight. The quadratic equation that describes the parabola is then used to correct the mass of unknowns by subtracting the deviation predicted by the quadratic equation from measured data. By subtracting the value of the parabola at each mass from the calibrated data, the accuracy of mass data points can be improved by factors of 10 or more. This method produces highly similar results whether or not initial ion velocity is accounted for in the calibration equation; consequently, there is no need to depend on that uncertain parameter when using the quadratic correction. This method can be used to correct the internally calibrated masses of protein digest peaks. The effect of nitrocellulose as a matrix additive is also briefly discussed, and it is shown that using nitrocellulose as an additive to the alpha-cyano-4-hydroxycinnamic acid (alphaCHCA) matrix does not significantly change initial ion velocity but does change the average position of ions relative to the sample electrode at the instant the extraction voltage is applied.

  18. Vacuum compatible sample positioning device for matrix assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry imaging

    SciTech Connect

    Aizikov, Konstantin; Lin, Tzu-Yung; Smith, Donald F.; Heeren, Ron M. A.; Chargin, David A.; Ivanov, Sergei; O'Connor, Peter B.

    2011-05-15

    The high mass accuracy and resolving power of Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS) make them ideal mass detectors for mass spectrometry imaging (MSI), promising to provide unmatched molecular resolution capabilities. The intrinsic low tolerance of FT-ICR MS to RF interference, however, along with typically vertical positioning of the sample, and MSI acquisition speed requirements present numerous engineering challenges in creating robotics capable of achieving the spatial resolution to match. This work discusses a two-dimensional positioning stage designed to address these issues. The stage is capable of operating in {approx}1 x 10{sup -8} mbar vacuum. The range of motion is set to 100 mm x 100 mm to accommodate large samples, while the positioning accuracy is demonstrated to be less than 0.4 micron in both directions under vertical load over the entire range. This device was integrated into three different matrix assisted laser desorption/ionization (MALDI) FT-ICR instruments and showed no detectable RF noise. The ''oversampling'' MALDI-MSI experiments, under which the sample is completely ablated at each position, followed by the target movement of the distance smaller than the laser beam, conducted on the custom-built 7T FT-ICR MS demonstrate the stability and positional accuracy of the stage robotics which delivers high spatial resolution mass spectral images at a fraction of the laser spot diameter.

  19. Vacuum compatible sample positioning device for matrix assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry imaging

    PubMed Central

    Aizikov, Konstantin; Smith, Donald F.; Chargin, David A.; Ivanov, Sergei; Lin, Tzu-Yung; Heeren, Ron M. A.; O’Connor, Peter B.

    2011-01-01

    The high mass accuracy and resolving power of Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS) make them ideal mass detectors for mass spectrometry imaging (MSI), promising to provide unmatched molecular resolution capabilities. The intrinsic low tolerance of FT-ICR MS to RF interference, however, along with typically vertical positioning of the sample, and MSI acquisition speed requirements present numerous engineering challenges in creating robotics capable of achieving the spatial resolution to match. This work discusses a two-dimensional positioning stage designed to address these issues. The stage is capable of operating in ∼1 × 10–8 mbar vacuum. The range of motion is set to 100 mm × 100 mm to accommodate large samples, while the positioning accuracy is demonstrated to be less than 0.4 micron in both directions under vertical load over the entire range. This device was integrated into three different matrix assisted laser desorption/ionization (MALDI) FT-ICR instruments and showed no detectable RF noise. The “oversampling” MALDI-MSI experiments, under which the sample is completely ablated at each position, followed by the target movement of the distance smaller than the laser beam, conducted on the custom-built 7T FT-ICR MS demonstrate the stability and positional accuracy of the stage robotics which delivers high spatial resolution mass spectral images at a fraction of the laser spot diameter. PMID:21639522

  20. [Determination of volatile organic compounds in ambient air by thermal desorption-gas chromatography-triple quadrupole tandem mass spectrometry].

    PubMed

    Feng, Lili; Hu, Xiaofang; Yu, Xiaojuan; Zhang, Wenying

    2016-02-01

    A method was established for the simultaneous determination of 23 volatile organic compounds (VOCs) in ambient air with combination of thermal desorption (TD) and gas chromatography-triple quadrupole tandem mass spectrometry (GC-MS/MS). The air samples were collected by active sampling method using Tenax-TA sorbent tubes, and desorbed by thermal desorption. The analytes were determined by GC-MS/MS in selected reaction monitoring (SRM) mode, and internal standard method was applied to quantify the VOCs. The results of all the 23 VOCs showed good linearities in low level (0. 01-1 ng) and high level (1-100 ng) with all the correlation coefficients (r2) more than 0. 99. The method quantification limits were between 0. 000 08-1 µg/m3. The method was validated by means of recovery experiments (n = 6) at three spiked levels of 2, 10 and 50 ng. The recoveries between 77% and 124% were generally obtained. The relative standard deviations (RSDs) in all cases were lower than 20%, except for chlorobenzene at the low spiked level. The developed method was applied to determine VOCs in ambient air collected at three sites in Shanghai. Several compounds, like benzene, toluene, ethylbenzene, m-xylenes, p-xylenes, styrene, 1, 2, 4-trimethylbenzene and hexachlorobutadiene were detected and confirmed in all the samples analyzed. The method is highly accurate, reliable and sensitive for monitoring the VOCs in ambient air. PMID:27382728

  1. Exploring Biosignatures Associated with Thenardite by Geomatrix-Assisted Laser Desorption/Ionization Fourier Transform Mass Spectrometry (GALDI-FTMS)

    SciTech Connect

    C. Doc Richardson; Nancy W. Hinman; Timothy R. McJunkin; Jill R. Scott

    2008-07-01

    Geomatrix-assisted laser desorption/ionization (GALDI) in conjunction with a Fourier transform mass spectrometer (FTMS) has been employed to determine how well bio/organic molecules associated with the mineral thenardite (Na2SO4) can be detected. GALDI is based on the ability of the mineral host to assist desorption and ionization of bio/organic molecules without additional sample preparation. When glycine was mixed with thenardite, glycine was deprotonated to produce C2H4NO2 at m/z 74.025. The combination of stearic acid with thenardite produced a complex cluster ion at m/z 390.258 in the negative mode, which was assigned a composition of C18H39O7Na . A natural sample of thenardite from Searles Lake in California also produced a peak at m/z 390.260. The bio/organic signatures in both the laboratory-based and natural samples were heterogeneously dispersed as revealed by chemical imaging. The detection limits for the stearic acid and thenardite combination was estimated to be 3 parts per trillion or ~7 zeptomoles per laser spot. Attempts to improve the signal-to-noise ratio by co-adding FTMS data predetermined to contain the biosignatures of interest revealed problems due to a lack of phase coherence between data sets.

  2. Functionalization of silicon nanowire arrays by silver nanoparticles for the laser desorption ionization mass spectrometry analysis of vegetable oils.

    PubMed

    Picca, Rosaria Anna; Calvano, Cosima Damiana; Lo Faro, Maria Josè; Fazio, Barbara; Trusso, Sebastiano; Ossi, Paolo Maria; Neri, Fortunato; D'Andrea, Cristiano; Irrera, Alessia; Cioffi, Nicola

    2016-09-01

    In this work, novel hybrid nanostructured surfaces, consisting of dense arrays of silicon nanowires (SiNWs) functionalized by Ag nanoparticles (AgNP/SiNWs), were used for the laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS) analysis of some typical unsaturated food components (e.g. squalene, oleic acid) to assess their MS performance. The synthesis of the novel platforms is an easy, cost-effective process based on the maskless wet-etching preparation at room temperature of SiNWs followed by their decoration with AgNPs, produced by pulsed laser deposition. No particular surface pretreatment or addition of organic matrixes/ionizers was necessary. Moreover, oil extracts (e.g. extra virgin olive oil, peanut oil) could be investigated on AgNP/SiNWs surfaces, revealing their different MS profiles. It was shown that such substrates operate at reduced laser energy, typically generating intense silver cluster ions and analyte adducts. A comparison with bare SiNWs was also performed, indicating the importance of AgNP density on NW surface. In this case, desorption/ionization on silicon was invoked as probable LDI mechanism. Finally, the influence of SiNW length and surface composition on MS results was assessed. The combination of typical properties of SiNWs (hydrophobicity, antireflectivity) with ionization ability of metal NPs can be a valid methodology for the further development of nanostructured surfaces in LDI-TOF MS applications. Copyright © 2016 John Wiley & Sons, Ltd.

  3. Matrix-Free UV-Laser Desorption Ionization Mass Spectrometry as a Versatile Approach for Accelerating Dereplication Studies on Lichens.

    PubMed

    Le Pogam, Pierre; Schinkovitz, Andreas; Legouin, Béatrice; Le Lamer, Anne-Cécile; Boustie, Joël; Richomme, Pascal

    2015-10-20

    The present study examined the suitability of laser desorption/ionization time-of-flight mass spectrometry (LDI-MS) for the rapid chemical fingerprinting of lichen extracts. Lichens are known to produce a wide array of secondary metabolites. Most of these compounds are unique to the symbiotic condition but some can be found in many species. Therefore, dereplication, that is, the rapid identification of known compounds within a complex mixture is crucial in the search for novel natural products. Over the past decade, significant advances were made in analytical techniques and profiling methods specifically adapted to crude lichen extracts, but LDI-MS has never been applied in this context. However, most classes of lichen metabolites have UV chromophores, which are quite similar to commercial matrix molecules used in matrix-assisted laser desorption ionization (MALDI). It is consequently postulated that these molecules could be directly detectable by matrix-free LDI-MS. The present study evaluated the versatility of this technique by investigating the LDI properties of a vast array of single lichen metabolites as well as lichen extracts of known chemical composition. Results from the LDI experiments were compared with those obtained by direct ESI-MS detection as well as LC-ESI-MS. It was shown that LDI ionization leads to strong molecular ion formation with little fragmentation, thus, facilitating straightforward spectra interpretation and representing a valuable alternative to time-consuming LC-MS analysis.

  4. Chemometric optimization of a low-temperature plasma source design for ambient desorption/ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Albert, Anastasia; Engelhard, Carsten

    2015-03-01

    Low-temperature plasmas (LTPs) are attractive sources for atomic and molecular mass spectrometry (MS). In the past, the LTP probe, which was first described by Harper et al., was used successfully for direct molecular mass spectrometric analysis with minimal sample pretreatment in a variety of applications. Unfortunately, the desorption/ionization source itself is commercially not available and custom-built LTP set-ups with varying geometry and operational configurations were utilized in the past. In the present study, a rapid chemometrics approach based on systematic experiments and multivariate data analysis was used to optimize the LTP probe geometry and positioning relative to the atmospheric-pressure inlet of a mass spectrometer. Several parameters were studied including the probe geometry, electrode configuration, quartz tube dimensions, probe positioning and operating conditions. It was found that the plasma-to-MS-inlet distance, the plasma-to-sample-plate distance, and the angle between the latter are very important. Additional effects on the analytical performance were found for the outer electrode width, the positioning of the electrodes, the inner diameter of the quartz tube, the quartz wall thickness, and the gas flow. All experiments were performed using additional heating of the sample to enhance thermal desorption and maximize the signal (T = 150 °C). After software-assisted optimization, attractive detection limits were achieved (e.g., 1.8 × 10- 7 mol/L for 4-acetamidothiophenol). Moreover, relative standard deviation (RSD) improved from values of up to 30% before optimization to < 15% RSD after the procedure was completed. This chemometrics approach for method optimization is not limited to LTP-MS and considered to be attractive for other plasma-based instrumentation as well.

  5. Nano-localized desorption and time-of-flight mass analysis using solely optical enhancement in the proximity of a scanning tunneling microscope tip

    NASA Astrophysics Data System (ADS)

    Ding, Yu; Micheletto, Ruggero; Okazaki, Satoshi; Otsuka, Koji

    2003-04-01

    The combination of scanning tunneling microscopy (STM) with time-of-flight mass system (TOF-MS) adds new information to STM imaging. In this study, an STM system has been combined with laser excitation and was used for desorption and ionization of surface molecules, without the use of any other external stimulus. Desorbed ions from confined areas were accelerated and detected by a TOF chamber. We demonstrate in this paper that the technique proposed enables desorption of superficial structures within a small area of approximately 5 nm diameter and simultaneous mass spectroscopy of the desorbed atoms.

  6. Effect of impurities on the matrix-assisted laser desorption mass spectra of single-stranded oligodeoxynucleotides.

    PubMed

    Shaler, T A; Wickham, J N; Sannes, K A; Wu, K J; Becker, C H

    1996-02-01

    The effect of impurities on the analysis of single-stranded DNA oligomers by the technique of matrix-assisted laser desorption/ionization with time-of-flight mass spectrometry has been studied using the matrix 3-hydroxypicolinic acid and 355-nm pulsed light. By mixing the DNA oligomers with different concentrations of impurities and recording mass spectra, limits are set on the tolerable level of a given impurity in a sample. The tolerance limits for sodium chloride, potassium chloride, sodium acetate, sodium fluoride, sodium dodecyl sulfate (SDS), and manganese(II) chloride were found to be approximately 10(-2) M. It was found that magnesium salts degraded the mass spectrum at much lower levels of 10(-4) M. The organic compounds tris(hydroxymethyl)aminomethane (Tris), urea, dithiothreitol (DTT), glycerol, and ethylenediaminetetraacetic acid (EDTA), when present as its ammonium salt, were tolerable at concentrations into the range of 0.25-0.5 M, while the organic polyamine compound spermine substantially degraded the mass spectrum at concentrations above 10(-2) M. When comparing these results for DNA analysis with previously reported limits for protein analysis, large differences are seen for some of the impurities tested. PMID:8712365

  7. Desorption electrospray ionization-high resolution mass spectrometry for the screening of veterinary drugs in cross-contaminated feedstuffs.

    PubMed

    Seró, Raquel; Núñez, Oscar; Bosch, Jaume; Grases, José M; Rodríguez, Pilar; Moyano, Encarnacion; Galceran, Martia Teresa

    2015-09-01

    In this study, a desorption electrospray ionization-high resolution mass spectrometry (DESI-HRMS) screening method was developed for fast identification of veterinary drugs in cross-contaminated feedstuffs. The reliable detection was performed working at high resolution (70,000 full width half maximum, FWHM) using an orbitrap mass analyzer. Among the optimized DESI parameters, the solvent (acetonitrile/water, 80:20, v/v) and the sample substrate (poly-tetrafluoroethylene, PTFE) were critical to obtain the best sensitivity. To analyze the solid feed samples, different approaches were tested and a simple solid-liquid extraction and the direct analysis of an aliquot (2 μL) of the extract after letting it dry on the PTFE printed spot provided the best results. The identification of the veterinary drugs (target and non-target) in the cross-contaminated feedstuffs based on the accurate mass measurement and the isotopic pattern fit was performed automatically using a custom-made database. The positive cross-contaminated feed samples were quantified by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The results obtained demonstrate that DESI-HRMS can be proposed as a fast and suitable screening method to identify positive cross-contaminated feedstuffs reducing the number of samples to be subsequently quantified by UHPLC-MS/MS, thus improving the productivity in quality control laboratories. PMID:26168975

  8. Differentiation of human kidney stones induced by melamine and uric acid using surface desorption atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Jia, Bin; Ouyang, Yongzhong; Sodhi, Rana N S; Hu, Bin; Zhang, Tingting; Li, Jianqiang; Chen, Huanwen

    2011-03-01

    Clinically obtained human kidney stones of different pathogenesis were dissolved in acetic acid/methanol solutions and then rapidly analyzed by surface desorption atmospheric pressure chemical ionization mass spectrometry (SDAPCI-MS) without any desalination treatment. The mass spectral fingerprints of six groups of kidney stone samples were rapidly recorded in the mass range of m/z 50-400. A set of ten melamine-induced kidney stone samples and nine uric acid derived kidney stone samples were successfully differentiated from other groups by principal component analysis of SDAPCI-MS fingerprints upon positive-ion detection mode. In contrast, the mass spectra recorded using negative-ion detection mode did not give enough information to differentiate those stone samples. The results showed that in addition to the melamine, the chemical compounds enwrapped in the melamine-induced kidney stone samples differed from other kidney stone samples, providing useful hints for studying on the formation mechanisms of melamine-induced kidney stones. This study also provides useful information on establishing a MS-based platform for rapid analysis of the melamine-induced human kidney stones at molecular levels.

  9. Desorption electrospray ionization-mass spectrometric analysis of low vapor pressure chemical particulates collected from a surface.

    PubMed

    Ewing, K J; Gibson, D; Sanghera, J; Miklos, F

    2015-01-01

    The collection of a low vapor pressure chemical simulant triethyl phosphate sorbed onto silica gel (TEP/SG) from a surface with subsequent analysis of the TEP/SG particulates using desorption electrospray ionization-mass spectrometry (DESI-MS) is described. Collection of TEP/SG particulates on a surface was accomplished using a sticky screen sampler composed of a stainless steel screen coated with partially polymerized polydimethylsiloxane (PDMS). DESI-MS analysis of TEP/SG particulates containing different percentages of TEP sorbed onto silica gel enabled the generation of response curves for the TEP ions m/z 155 and m/z 127. Using the response curves the calculation of the mass of TEP in a 25 wt% sample of TEP/SG was calculated, results show that the calculated mass of TEP was 14% different from the actual mass of TEP in the sample using the m/z 127 TEP ion response curve. Detection limits for the TEP vapor and TEP/SG particulates were calculated to be 4 μg and 6 particles, respectively.

  10. Desorption electrospray ionization-high resolution mass spectrometry for the screening of veterinary drugs in cross-contaminated feedstuffs.

    PubMed

    Seró, Raquel; Núñez, Oscar; Bosch, Jaume; Grases, José M; Rodríguez, Pilar; Moyano, Encarnacion; Galceran, Martia Teresa

    2015-09-01

    In this study, a desorption electrospray ionization-high resolution mass spectrometry (DESI-HRMS) screening method was developed for fast identification of veterinary drugs in cross-contaminated feedstuffs. The reliable detection was performed working at high resolution (70,000 full width half maximum, FWHM) using an orbitrap mass analyzer. Among the optimized DESI parameters, the solvent (acetonitrile/water, 80:20, v/v) and the sample substrate (poly-tetrafluoroethylene, PTFE) were critical to obtain the best sensitivity. To analyze the solid feed samples, different approaches were tested and a simple solid-liquid extraction and the direct analysis of an aliquot (2 μL) of the extract after letting it dry on the PTFE printed spot provided the best results. The identification of the veterinary drugs (target and non-target) in the cross-contaminated feedstuffs based on the accurate mass measurement and the isotopic pattern fit was performed automatically using a custom-made database. The positive cross-contaminated feed samples were quantified by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The results obtained demonstrate that DESI-HRMS can be proposed as a fast and suitable screening method to identify positive cross-contaminated feedstuffs reducing the number of samples to be subsequently quantified by UHPLC-MS/MS, thus improving the productivity in quality control laboratories.

  11. Detection of Posaconazole by Surface-Assisted Laser Desorption/Ionization Mass Spectrometry with Dispersive Liquid-Liquid Microextraction

    NASA Astrophysics Data System (ADS)

    Lin, Sheng-Yu; Chen, Pin-Shiuan; Chang, Sarah Y.

    2015-03-01

    A simple, rapid, and sensitive method for the detection of posaconazole using dispersive liquid-liquid microextraction (DLLME) coupled to surface-assisted laser desorption/ionization mass spectrometric detection (SALDI/MS) was developed. After the DLLME, posaconazole was detected using SALDI/MS with colloidal gold and α-cyano-4-hydroxycinnamic acid (CHCA) as the co-matrix. Under optimal extraction and detection conditions, the calibration curve, which ranged from 1.0 to 100.0 nM for posaconazole, was observed to be linear. The limit of detection (LOD) at a signal-to-noise ratio of 3 was 0.3 nM for posaconazole. This novel method was successfully applied to the determination of posaconazole in human urine samples.

  12. On plate graphite supported sample processing for simultaneous lipid and protein identification by matrix assisted laser desorption ionization mass spectrometry.

    PubMed

    Calvano, Cosima Damiana; van der Werf, Inez Dorothé; Sabbatini, Luigia; Palmisano, Francesco

    2015-05-01

    The simultaneous identification of lipids and proteins by matrix assisted laser desorption ionization-mass spectrometry (MALDI-MS) after direct on-plate processing of micro-samples supported on colloidal graphite is demonstrated. Taking advantages of large surface area and thermal conductivity, graphite provided an ideal substrate for on-plate proteolysis and lipid extraction. Indeed proteins could be efficiently digested on-plate within 15 min, providing sequence coverages comparable to those obtained by conventional in-solution overnight digestion. Interestingly, detection of hydrophilic phosphorylated peptides could be easily achieved without any further enrichment step. Furthermore, lipids could be simultaneously extracted/identified without any additional treatment/processing step as demonstrated for model complex samples such as milk and egg. The present approach is simple, efficient, of large applicability and offers great promise for protein and lipid identification in very small samples.

  13. Efficient sample preparation in immuno-matrix-assisted laser desorption/ionization mass spectrometry using acoustic trapping

    PubMed Central

    Hammarström, Björn; Yan, Hong; Nilsson, Johan; Ekström, Simon

    2013-01-01

    Acoustic trapping of minute bead amounts against fluid flow allows for easy automation of multiple assay steps, using a convenient aspirate/dispense format. Here, a method based on acoustic trapping that allows sample preparation for immuno-matrix-assisted laser desorption/ionization mass spectrometry using only half a million 2.8 μm antibody covered beads is presented. The acoustic trapping is done in 200 × 2000 μm2 glass capillaries and provides highly efficient binding and washing conditions, as shown by complete removal of detergents and sample processing times of 5-10 min. The versatility of the method is demonstrated using an antibody against Angiotensin I (Ang I), a peptide hormone involved in hypotension. Using this model system, the acoustic trapping was efficient in enriching Angiotensin at 400 pM spiked in plasma samples. PMID:24404012

  14. Recent Advances in Bacteria Identification by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Using Nanomaterials as Affinity Probes

    PubMed Central

    Chiu, Tai-Chia

    2014-01-01

    Identifying trace amounts of bacteria rapidly, accurately, selectively, and with high sensitivity is important to ensuring the safety of food and diagnosing infectious bacterial diseases. Microbial diseases constitute the major cause of death in many developing and developed countries of the world. The early detection of pathogenic bacteria is crucial in preventing, treating, and containing the spread of infections, and there is an urgent requirement for sensitive, specific, and accurate diagnostic tests. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is an extremely selective and sensitive analytical tool that can be used to characterize different species of pathogenic bacteria. Various functionalized or unmodified nanomaterials can be used as affinity probes to capture and concentrate microorganisms. Recent developments in bacterial detection using nanomaterials-assisted MALDI-MS approaches are highlighted in this article. A comprehensive table listing MALDI-MS approaches for identifying pathogenic bacteria, categorized by the nanomaterials used, is provided. PMID:24786089

  15. Selective analysis of lipids by thin-layer chromatography blot matrix-assisted laser desorption/ionization imaging mass spectrometry.

    PubMed

    Zaima, Nobuhiro; Goto-Inoue, Naoko; Adachi, Kohsuke; Setou, Mitsutoshi

    2011-01-01

    Thin-layer chromatography (TLC) is an essential method for food composition analyses such as lipid nutrition analysis. TLC can be used to obtain information about the lipid composition of foods; however, it cannot be used for analyses at the molecular level. Recently we developed a new method that combines matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS) with TLC-blotting (TLC-Blot-MALDI-IMS). The combination of MALDI-IMS and TLC blotting enabled detailed and sensitive analyses of lipids. In this study, we applied TLC-Blot-MALDI-IMS for analysis of major phospholipids extracted from bluefin tuna. We showed that TLC-Blot-MALDI-IMS analysis could visualize and identify major phospholipids such as phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidylcholine, and sphingomyelin.

  16. 5-Methoxysalicylic Acid Matrix for Ganglioside Analysis with Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Lee, Dongkun; Cha, Sangwon

    2015-03-01

    In this note, we report that high quality ganglioside profiles with minimal loss of sialic acid residues can be obtained in the positive ion mode by using a 5-methoxysalicylic acid (MSA) matrix for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS). Our results showed that MSA produced much less sialic acid losses from gangliosides than DHB, although MSA and DHB are differ only by their functional groups at their 5-positions (-OH for DHB and -OCH3 for MSA). Furthermore, our data also demonstrated that addition of an alkali metal additive was effective for simplifying ganglioside profiles, but not necessary for stabilizing glycosidic bonds of gangliosides if MSA was used as a matrix. This suggests that MALDI MS with MSA has a potential to gain additional benefits from the positive-ion mode analyses without losing performance in ganglioside profiling.

  17. Matrix assisted laser desorption/ionization-mass spectrometry imaging (MALDI-MSI) for direct visualization of plant metabolites in situ

    DOE PAGESBeta

    Sturtevant, Drew; Lee, Young -Jin; Chapman, Kent D.

    2015-11-22

    Direct visualization of plant tissues by matrix assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) has revealed key insights into the localization of metabolites in situ. Recent efforts have determined the spatial distribution of primary and secondary metabolites in plant tissues and cells. Strategies have been applied in many areas of metabolism including isotope flux analyses, plant interactions, and transcriptional regulation of metabolite accumulation. Technological advances have pushed achievable spatial resolution to subcellular levels and increased instrument sensitivity by several orders of magnitude. Furthermore, it is anticipated that MALDI-MSI and other MSI approaches will bring a new level of understanding tomore » metabolomics as scientists will be encouraged to consider spatial heterogeneity of metabolites in descriptions of metabolic pathway regulation.« less

  18. Screening of the Binding of Small Molecules to Proteins by Desorption Electrospray Ionization Mass Spectrometry Combined with Protein Microarray

    NASA Astrophysics Data System (ADS)

    Yao, Chenxi; Wang, Tao; Zhang, Buqing; He, Dacheng; Na, Na; Ouyang, Jin

    2015-11-01

    The interaction between bioactive small molecule ligands and proteins is one of the important research areas in proteomics. Herein, a simple and rapid method is established to screen small ligands that bind to proteins. We designed an agarose slide to immobilize different proteins. The protein microarrays were allowed to interact with different small ligands, and after washing, the microarrays were screened by desorption electrospray ionization mass spectrometry (DESI MS). This method can be applied to screen specific protein binding ligands and was shown for seven proteins and 34 known ligands for these proteins. In addition, a high-throughput screening was achieved, with the analysis requiring approximately 4 s for one sample spot. We then applied this method to determine the binding between the important protein matrix metalloproteinase-9 (MMP-9) and 88 small compounds. The molecular docking results confirmed the MS results, demonstrating that this method is suitable for the rapid and accurate screening of ligands binding to proteins.

  19. Matrix-assisted laser desorption/ionization mass spectrometry of neutral and acidic oligosaccharides with collision-induced dissociation.

    PubMed

    Mechref, Y; Baker, A G; Novotny, M V

    1998-12-15

    Using ribonuclease B and human alpha 1-acid glycoprotein (AGP) as model glycoproteins, matrix-assisted laser desorption/ionization (MALDI) mass spectrometry with collision-induced dissociation (CID) is validated here as an effective tool for oligosaccharide sequencing. The spectra acquired for high-mannose and complex oligosaccharide structures show characteristic fragments resulting from cleavages of the glycosidic bonds and a few cross-ring cleavages. Esterification of the sialic acid residues is essential in stabilizing the acidic N-linked oligosaccharides. An important analytical feature observed in all acquired spectra is the occurrence of cleavages on the same antenna up to the branching point, as deduced from the absence of fragmentation due to the simultaneous cleavages on two or more antennas.

  20. Efficient sample preparation in immuno-matrix-assisted laser desorption/ionization mass spectrometry using acoustic trapping.

    PubMed

    Hammarström, Björn; Yan, Hong; Nilsson, Johan; Ekström, Simon

    2013-01-01

    Acoustic trapping of minute bead amounts against fluid flow allows for easy automation of multiple assay steps, using a convenient aspirate/dispense format. Here, a method based on acoustic trapping that allows sample preparation for immuno-matrix-assisted laser desorption/ionization mass spectrometry using only half a million 2.8 μm antibody covered beads is presented. The acoustic trapping is done in 200 × 2000 μm(2) glass capillaries and provides highly efficient binding and washing conditions, as shown by complete removal of detergents and sample processing times of 5-10 min. The versatility of the method is demonstrated using an antibody against Angiotensin I (Ang I), a peptide hormone involved in hypotension. Using this model system, the acoustic trapping was efficient in enriching Angiotensin at 400 pM spiked in plasma samples.

  1. Polyhydroxyanthraquinones as Quorum Sensing Inhibitors from the Guttates of Penicillium restrictum and Their Analysis by Desorption Electrospray Ionization Mass Spectrometry

    PubMed Central

    2015-01-01

    The endophytic fungus Penicillium restrictum was isolated from the stems of a milk thistle (Silybum marianum) plant. In culture, the fungus produced distinct red guttates, which have been virtually uninvestigated, particularly from the standpoint of chemistry. Hence, this study examined the chemical mycology of P. restrictum and, in doing so, uncovered a series of both known and new polyhydroxyanthraquinones (1–9). These compounds were quorum sensing inhibitors in a clinical isolate of methicillin-resistant Staphylococcus aureus (MRSA), with IC50 values ranging from 8 to 120 μM, suggesting antivirulence potential for the compounds. Moreover, the spatial and temporal distribution of the polyhydroxyanthraquinones was examined in situ via desorption electrospray ionization–mass spectrometry (DESI-MS) imaging, demonstrating the first application of this technique to a guttate-forming fungus and revealing both the concentration of secondary metabolites at the ventral surface of the fungus and their variance in colonies of differing ages. PMID:24911880

  2. Analysis and Quantitation of Glycated Hemoglobin by Matrix Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Hattan, Stephen J.; Parker, Kenneth C.; Vestal, Marvin L.; Yang, Jane Y.; Herold, David A.; Duncan, Mark W.

    2016-03-01

    Measurement of glycated hemoglobin is widely used for the diagnosis and monitoring of diabetes mellitus. Matrix assisted laser desorption/ionization (MALDI) time of flight (TOF) mass spectrometry (MS) analysis of patient samples is used to demonstrate a method for quantitation of total glycation on the β-subunit of hemoglobin. The approach is accurate and calibrated with commercially available reference materials. Measurements were linear (R2 > 0.99) across the clinically relevant range of 4% to 20% glycation with coefficients of variation of ≤ 2.5%. Additional and independent measurements of glycation of the α-subunit of hemoglobin are used to validate β-subunit glycation measurements and distinguish hemoglobin variants. Results obtained by MALDI-TOF MS were compared with those obtained in a clinical laboratory using validated HPLC methodology. MALDI-TOF MS sample preparation was minimal and analysis times were rapid making the method an attractive alternative to methodologies currently in practice.

  3. Identification of adulteration in milk by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Cozzolino, R; Passalacqua, S; Salemi, S; Malvagna, P; Spina, E; Garozzo, D

    2001-09-01

    The development is described of a rapid, simply and accurate analytical method aimed at evaluating both the presence of cow milk in either raw ewe and water buffalo milk samples employed in industrial processes and the addition of powdered milk to samples of fresh raw milk, using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). The presence of adulteration is defined by evaluating the protein patterns coming from the most abundant whey proteins, alpha-lactalbumin and beta-lactoglobulin, used as molecular markers. As no pretreatment of the milk samples is required and owing to the speed and ease of use of MALDI-MS the proposed analytical protocol can be used as a routine strategy for the identification of possible adulteration of the raw fresh milk samples that the dairy industry receives from producers every day.

  4. Developments and Applications of Electrophoresis and Small Molecule Laser Desorption Ionization Mass Spectrometry

    SciTech Connect

    Zhang, Hui

    2007-01-01

    Ultra-sensitive native fluorescence detection of proteins with miniaturized one- and two-dimensional polyacrylamide gel electrophoresis was achieved with laser side-entry excitation, which provides both high excitation power and low background level. The detection limit for R-phycoerythrin protein spots in 1-D SDS-PAGE was as low as 15 fg, which corresponds to 40 thousand molecules only. The average detection limit of six standard native proteins was 5 pg per band and the dynamic range spanned more than 3 orders of magnitude. Approximately 150 protein spots from 30 ng of total Escherichia coli extraction were detected on a 0.8 cm x 1 cm gel in two-dimensional separation. Estrogen-DNA adducts as 4-OHE1(E2)-1-N3Ade and 4-OHEI(E2)-2-NacCys were hypothesized as early risk assessment of prostate and breast cancers. Capillary electrophoresis, luminescence/absorption spectroscopy and LC-MS were used to characterize and detect these adducts. Monoclonal antibodies against each individual adduct were developed and used to enrich such compounds from urine samples of prostate and breast cancer patients as well as healthy people. Adduct 4-OHE1-1-N3Ade was detected at much higher level in urine from subjects with prostate cancer patients compared to healthy males. The same adduct and 4-OHEI-2-NacCys were also detected at a much higher level in urine from a woman with breast carcinoma than samples from healthy controls. These two DNA adducts may serve as novel biomarkers for early diagnostic of cancers. The adsorption properties of R-phycoerythrin (RPE), on the fused-silica surface were studied using capillary electrophoresis (CE) and single molecule spectroscopy. The band shapes and migration times were measured in CE. Adsorption and desorption events were recorded at the single-molecule level by imaging of the evanescent-field layer using total internal reflection. The adsorbed RPE molecules on the fused-silica prism surface were

  5. Development of thermal desorption gas chromatography/mass spectrometry as a rapid method for ambient particulate characterization

    NASA Astrophysics Data System (ADS)

    Sheya, Sue Anne N.

    A direct thermal desorption gas chromatography/mass spectrometry (TD GC/MS) method for air particulate matter (PM) analysis of volatile and semivolatile organic compounds was investigated. This technique uses a specially designed microdesorption GC inlet utilizing an inductively heated ferromagnetic foil with a Curie point temperature suitable for desorption, which can accommodate microgram amounts of material deposited on a thin strip of quartz fiber filter. Liquid or solid samples can be rapidly desorbed within 10 s at 315°C, followed by 30--40 min of chromatography time. The results obtained by this technique were found to be statistically equivalent to those obtained by the conventional solvent extraction gas chromatography/mass spectrometry (SX GC/MS) method for analysis of aromatic and n alkane standards, single source soot particles, and PM 10 filter samples. Correlations between injecting an extract, desorbing an extract, and desorbing particles averaged R = 0.94, with a three way correlation averaging R = 0.97. High volume sampling conducted at 12 spatially distributed sites located along the US/Mexican border of the El Paso/Juarez metroplex supplied 24h PM 10 filters for an investigation combining thermal desorption with a rapid online chemical derivatization procedure, and multivariate methods of source attribution using principal component and canonical correlation analysis of the resultant chemical markers. Four major combustion related PM emission sources were revealed at these sites: automotive, waste burning, biomass burning and meat cooking. A second investigation conducted in the same area used mediumvolume sampling to collect 2 h timeresolved PM 10 receptor samples for TD GC/MS analysis. Additionally, 2 h samples for inorganic analysis, multichannel particle size distribution measurements, and meteorological data were collected enabling generation of circadian PM multicharacterization profiles. Factor analysis based receptor modeling using

  6. Droplet dynamics and ionization mechanisms in desorption electrospray ionization mass spectrometry.

    PubMed

    Venter, Andre; Sojka, Paul E; Cooks, R Graham

    2006-12-15

    A droplet pickup and other mechanisms have been suggested for the ionization of biomolecules like peptides and proteins by desorption electrospray ionization. To verify this hypothesis phase Doppler particle analysis was used to study the sizes and velocities of droplets involved in DESI. It was found that impacting droplets typically have velocities of 120 m/s and average diameters of 2-4 microm. Small differences in sprayer construction influence the operating conditions at which droplets of these dimensions are produced. Under these conditions, the kinetic energy per impacting water molecule is less than 0.6 meV and sputtering through momentum transfer during collisions or ionization by other electronic processes is unlikely. Droplets arrive at the surface with velocities well below the speed of sound in common materials, thereby excluding the possibility of ionization by shockwave formation. Some droplets appear to roll along the surface, increasing contact time and presumably the amount of material that is taken up into droplets during conditions typical of the DESI experiment.

  7. Direct Analysis of Textile Fabrics and Dyes Using IR Matrix-Assisted Laser Desorption Electrospray Ionization (MALDESI) Mass Spectrometry

    PubMed Central

    Cochran, Kristin H.; Barry, Jeremy A.; Muddiman, David C.; Hinks, David

    2012-01-01

    The forensic analysis of textile fibers uses a variety of techniques from microscopy to spectroscopy. One such technique that is often used to identify the dye(s) within the fiber is mass spectrometry (MS). In the traditional MS method, the dye must be extracted from the fabric and the dye components are separated by chromatography prior to mass spectrometric analysis. Direct analysis of the dye from the fabric allows the omission of the lengthy sample preparation involved in extraction, thereby significantly reducing the overall analysis time. Herein, a direct analysis of dyed textile fabric was performed using the infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) source for MS. In MALDESI, an IR laser with wavelength tuned to 2.94 μm is used to desorb the dye from the fabric sample with the aid of water as the matrix. The desorbed dye molecules are then post-ionized by electrospray ionization (ESI). A variety of dye classes were analyzed from various fabrics with little to no sample preparation allowing for the identification of the dye mass and in some cases the fiber polymer. Those dyes that were not detected using MALDESI were also not observed by direct infusion ESI of the dye standard. PMID:23237031

  8. Direct analysis of textile fabrics and dyes using infrared matrix-assisted laser desorption electrospray ionization mass spectrometry.

    PubMed

    Cochran, Kristin H; Barry, Jeremy A; Muddiman, David C; Hinks, David

    2013-01-15

    The forensic analysis of textile fibers uses a variety of techniques from microscopy to spectroscopy. One such technique that is often used to identify the dye(s) within the fiber is mass spectrometry (MS). In the traditional MS method, the dye must be extracted from the fabric and the dye components are separated by chromatography prior to mass spectrometric analysis. Direct analysis of the dye from the fabric allows the omission of the lengthy sample preparation involved in extraction, thereby significantly reducing the overall analysis time. Herein, a direct analysis of dyed textile fabric was performed using the infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) source for MS. In MALDESI, an IR laser with wavelength tuned to 2.94 μm is used to desorb the dye from the fabric sample with the aid of water as the matrix. The desorbed dye molecules are then postionized by electrospray ionization (ESI). A variety of dye classes were analyzed from various fabrics with little to no sample preparation allowing for the identification of the dye mass and in some cases the fiber polymer. Those dyes that were not detected using MALDESI were also not observed by direct infusion ESI of the dye standard. PMID:23237031

  9. Analysis of Polycyclic Aromatic Hydrocarbons Using Desorption Atmospheric Pressure Chemical Ionization Coupled to a Portable Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Jjunju, Fred P. M.; Maher, Simon; Li, Anyin; Badu-Tawiah, Abraham K.; Taylor, Stephen; Graham Cooks, R.

    2015-02-01

    Desorption atmospheric pressure chemical ionization (DAPCI) is implemented on a portable mass spectrometer and applied to the direct detection of polycyclic aromatic hydrocarbons (PAHs) and alkyl substituted benzenes. The presence of these compounds in the environment poses a significant threat to the health of both humans and wildlife because of their carcinogenic, toxic, and mutagenic properties. As such, instant detection outside of the laboratory is of particular importance to allow in-situ measurement at the source. Using a rapid, high throughput, miniature, handheld mass spectrometer, several alkyl substituted benzenes and PAHs (i.e., 1,2,3,5-tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, fluoranthene, anthracene, benzo[ k]fluoranthene, dibenz[ a,h]anthracene, acenaphthene, indeno[1,2,3-c,d]pyrene, 9-ethylfluorene, and 1-benzyl-3-methyl-naphthalene) were identified and characterized using tandem mass spectrometry (MS/MS) from ambient surfaces, in the open air. This method can provide almost instantaneous information while minimizing sample preparation, which is advantageous in terms of both cost and simplicity of analysis. This MS-based technique is applicable to a wide range of environmental organic molecules.

  10. Direct analysis of textile fabrics and dyes using infrared matrix-assisted laser desorption electrospray ionization mass spectrometry.

    PubMed

    Cochran, Kristin H; Barry, Jeremy A; Muddiman, David C; Hinks, David

    2013-01-15

    The forensic analysis of textile fibers uses a variety of techniques from microscopy to spectroscopy. One such technique that is often used to identify the dye(s) within the fiber is mass spectrometry (MS). In the traditional MS method, the dye must be extracted from the fabric and the dye components are separated by chromatography prior to mass spectrometric analysis. Direct analysis of the dye from the fabric allows the omission of the lengthy sample preparation involved in extraction, thereby significantly reducing the overall analysis time. Herein, a direct analysis of dyed textile fabric was performed using the infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) source for MS. In MALDESI, an IR laser with wavelength tuned to 2.94 μm is used to desorb the dye from the fabric sample with the aid of water as the matrix. The desorbed dye molecules are then postionized by electrospray ionization (ESI). A variety of dye classes were analyzed from various fabrics with little to no sample preparation allowing for the identification of the dye mass and in some cases the fiber polymer. Those dyes that were not detected using MALDESI were also not observed by direct infusion ESI of the dye standard.

  11. Molecular weight determination of hyaluronic acid by gel filtration chromatography coupled to matrix-assisted laser desorption ionization mass spectrometry.

    PubMed

    Yeung, B; Marecak, D

    1999-08-13

    An analytical approach has been described for the molecular weight characterization of enzymatically degraded hyaluronic acid (HA). The approach involved the combined use of aqueous gel filtration chromatography (GFC) with matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS). Microfractions were collected across an eluting peak from the chromatography system, followed by mass spectrometric analysis of these narrow fractions. The molecular mass determined by MALDI-MS and the signal obtained from the chromatography established a calibration curve for other hyaluronic acid samples analyzed by this GFC system. Results of one HA sample were obtained from both the calibration curve and direct fraction-by-fraction MALDI-MS analysis, and comparison of these results showed reasonable agreement. In contrast, molecular weights resulted from external calibration using dextran and pullullan standards showed drastically different numbers. Therefore, the GFC-MALDI-MS approach is a reliable method for the molecular weight characterization of polydisperse polysaccharides for which suitable calibration standards are unavailable for conventional GFC analysis. PMID:10481993

  12. Improved procedure for dendrimer-based mass calibration in matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry.

    PubMed

    Gross, Jürgen H

    2016-08-01

    A procedure is described that results in a substantial increase in signal intensity and in improved accuracy of positive-ion mass calibration when using commercially available kits of monodisperse dendrimers (SpheriCal(®)) in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS). The peak intensities are amplified by an admixture of 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) matrix to the kits comprising of 9-nitroanthracene matrix, sodium trifluoroacetate, and four dendrimers. Boosted ion formation then permits lower laser fluence to be used and thus yields enhanced mass resolution. Further, the number of reference peaks is doubled by doping the sample preparation with cesium ions. This results in four [M+Cs](+) ion signals in addition to four [M+Na](+) ion signals provided by the standard kit. Overall, the modified procedure notably reduces the consumption of the expensive calibration standard kits, while it increases mass resolution and enables the use of an advanced calibration algorithm requiring at least six reference peaks. Graphical abstract A dendrimer-based mass calibration for MALDI-TOF-MS can be improved by adding a DCTB matrix and doping the sample preparation with Cs(+) ions. Having eight rather than just four reference peaks reduces the average mass error of the calibration curve about fivefold. PMID:27317254

  13. Raman spectroscopy and laser desorption mass spectrometry for minimal destructive forensic analysis of black and color inkjet printed documents.

    PubMed

    Heudt, Laetitia; Debois, Delphine; Zimmerman, Tyler A; Köhler, Laurent; Bano, Fouzia; Partouche, Franck; Duwez, Anne-Sophie; Gilbert, Bernard; De Pauw, Edwin

    2012-06-10

    Inkjet ink analysis is the best way to discriminate between printed documents, or even though more difficult, to connect an inkjet printed document with a brand or model of printers. Raman spectroscopy and laser desorption mass spectrometry (LDMS) have been demonstrated as powerful tools for dyes and pigments analysis, which are ink components. The aim of this work is to evaluate the aforementioned techniques for inkjet inks analysis in terms of discriminating power, information quality, and nondestructive capability. So, we investigated 10 different inkjet ink cartridges (primary colors and black), 7 from the HP manufacturer and one each from Epson, Canon and Lexmark. This paper demonstrates the capabilities of three methods: Raman spectroscopy, LDMS and MALDI-MS. Raman spectroscopy, as it is preferable to try the nondestructive approach first, is successfully adapted to the analysis of color printed documents in most cases. For analysis of color inkjet inks by LDMS, we show that a MALDI matrix (9-aminoacridine, 9AA) is needed to desorb and to ionize dyes from most inkjet inks (except Epson inks). Therefore, a method was developed to apply the 9AA MALDI matrix directly onto the piece of paper while avoiding analyte spreading. The obtained mass spectra are very discriminating and lead to information about ink additives and paper compositions. Discrimination of black inkjet printed documents is more difficult because of the common use of carbon black as the principal pigment. We show for the first time the possibility to discriminate between two black-printed documents coming from different, as well as from the same, manufacturers. Mass spectra recorded from black inks in positive ion mode LDMS detect polyethylene glycol polymers which have characteristic mass distributions and end groups. Moreover, software has been developed for rapid and objective comparison of the low mass range of these positive mode LDMS spectra which have characteristic unknown peaks. PMID

  14. Matrix-assisted laser desorption ionization-time of flight mass spectrometry can accurately differentiate Aeromonas dhakensis from A. hydrophila, A. caviae, and A. veronii.

    PubMed

    Chen, Po-Lin; Lee, Tai-Fen; Wu, Chi-Jung; Teng, Shih-Hua; Teng, Lee-Jene; Ko, Wen-Chien; Hsueh, Po-Ren

    2014-07-01

    Among 217 Aeromonas isolates identified by sequencing analysis of their rpoB genes, the accuracy rates of identification of A. dhakensis, A. hydrophila, A. veronii, and A. caviae were 96.7%, 90.0%, 96.7%, and 100.0%, respectively, by the cluster analysis of spectra generated by matrix-assisted laser desorption ionization-time of flight mass spectrometry.

  15. Evaluation of matrix-assisted laser desorption ionization-time-of-flight mass spectrometry for species identification of nonfermenting Gram-negative bacilli.

    PubMed

    Almuzara, Marisa; Barberis, Claudia; Traglia, Germán; Famiglietti, Angela; Ramirez, Maria Soledad; Vay, Carlos

    2015-05-01

    Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) to identify 396 Nonfermenting Gram-Negative Bacilli clinical isolates was evaluated in comparison with conventional phenotypic tests and/or molecular methods. MALDI-TOF MS identified to species level 256 isolates and to genus or complex level 112 isolates. It identified 29 genera including uncommon species.

  16. THE USE OF MATRIX-ASSISTED LASER DESORPTION/IONIZATION-MASS SPECTROMETRY FOR THE IDENTIFICATION OF AEROMONAS ISOLATES OBTAINED FROM WATER DISTRIBUTION SYSTEMS

    EPA Science Inventory

    Matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) has long been established as a tool by which microorganisms can be characterized and identified. EPA is investigating the potential of using this technology as a way to rapidly identify Aeromonas species fo...

  17. THERMAL DESORPTION MASS SPECTROMETRIC ANALYSIS OF ORGANIC AEROSOL FORMED FROM REACTIONS OF 1-TETRADECENE AND O3 IN THE PRESENCE OF ALCOHOLS AND CARBOXYLIC ACIDS. (R826235)

    EPA Science Inventory

    The chemistry of secondary organic aerosol formation from reactions of
    1-tetradecene and O3 in dry air in the presence of excess alcohols
    and carboxylic acids was investigated in an environmental chamber using a
    thermal desorption particle beam mass spec...

  18. Analysis of Phospholipid Mixtures from Biological Tissues by Matrix-Assisted Laser Desorption and Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS): A Laboratory Experiment

    ERIC Educational Resources Information Center

    Eibisch, Mandy; Fuchs, Beate; Schiller, Jurgen; Sub, Rosmarie; Teuber, Kristin

    2011-01-01

    Matrix-assisted laser desorption and ionization time-of-flight mass spectrometry (MALDI-TOF MS) is increasingly used to investigate the phospholipid (PL) compositions of tissues and body fluids, often without previous separation of the total mixture into the individual PL classes. Therefore, the questions of whether all PL classes are detectable…

  19. Determination of off-flavor compounds, 2-methylisoborneol and geosmin, in salmon fillets using stir bar sorptive extraction–thermal desorption coupled with gas chromatography–mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A sensitive and solvent-less method for the determination of musty and earthy off-flavor compounds, 2-methylisoborneol (MIB) and geosmin (GSM), in salmon tissue was developed using stir bar sorptive extraction -thermal desorption coupled with gas chromatography -mass spectrometry (SBSE -TD -GCMS). M...

  20. The potential of matrix-assisted laser desorption/ionization mass spectrometry in the quality control of water buffalo mozzarella cheese.

    PubMed

    Angeletti, R; Gioacchini, A M; Seraglia, R; Piro, R; Traldi, P

    1998-06-01

    Adulteration by addition of bovine milk to water buffalo milk employed for mozzarella cheese production is often observed. Water buffalo milk and mozzarella cheese were analysed by matrix-assisted laser desorption/ionization mass spectrometry in order to achieve their rapid and accurate characterization and to evaluate possible fraudulence in mozzarella cheese production.

  1. Detection of Biosignatures in Natural and Microbial Cultured Jarosites Using Laser- Desorption Fourier Transform Mass Spectrometry: Implications for Astrobiology

    NASA Astrophysics Data System (ADS)

    Kotler, J.; Hinman, N. W.; Yan, B.; Stoner, D. L.; Scott, J. R.

    2006-12-01

    The jarosite group minerals have received increasing attention since the discovery by the Mars Exploration Rover-Opportunity of jarosite on the Martian surface. The general chemical formula for jarosite is XFe3(SO4)2(OH)6 where the X represents both monovalent and divalent cations that can occupy the axial positions in the crystal structure. Commonly found ions include K+, Na+, H3O+, NH4+, and Pb2+ with reports of other large ions occupying this position in the literature. Modeling efforts have been performed to confirm that jarosite has the ability to incorporate a variety of "foreign" cations. The minerals unique ability to incorporate various large ions in its structure and its association with biological activity in terrestrial environments has lead to investigations regarding its use as an indicator of aqueous and/or biological activity. The use of laser desorption Fourier transform mass spectrometry (LD-FTMS) has revealed the presence of organic matter including the amino acid, glycine, in several jarosite samples from various worldwide locations. Iron precipitates derived from acidophilic microbial cultures were also analyzed. Using attenuated total reflectance infrared spectroscopy (ATR-IR), signals indicative of microbes or microbial exudates were weak and ambiguous. In contrast, LD-FTMS clearly detected bioorganic constituents in some desorption spots. However, the signals were sporadic and required the laser scanning/imaging capability of our laboratory built system to locate the microbial signatures in the heterogeneous samples. The ability to observe these bioorganic signatures in jarosite samples using the instrumental technique employed in this study furthers the goals of planetary geologists to determine whether signs of life (e.g., presence of biomolecules or biomolecule precursors) can be detected in the rock record of terrestrial and extraterrestrial samples.

  2. Detection of drugs in lifted cyanoacrylate-developed latent fingermarks using two laser desorption/ionisation mass spectrometric methods.

    PubMed

    Sundar, Latha; Rowell, Frederick

    2014-02-01

    This paper describes a method for lifting cyanoacrylate (CNA)-developed latent fingermarks from a glass surface and the detection of five drugs in lifted marks from fingers that had been in contact with the drugs, using Surface Assisted Laser Desorption Ionisation Time of Flight Mass Spectrometry (SALDI-TOF-MS) or Matrix Assisted Laser Desorption Ionisation TOF-MS (MALDI-TOF-MS). Two drugs of abuse (cocaine and methadone) and three therapeutic drugs (aspirin, paracetamol and caffeine) were used as contact residues. Latent fingermarks spiked with the drugs were subjected to CNA fuming followed by dusting with ARRO SupraNano™ MS black magnetic powder (SALDI-TOF-MS) or 2,5-dihydroxybenzoic acid (DHB) (MALDI-TOF-MS). The dusted mark was then exposed to solvent vapour before lifting with a commercial fingerprint lifting tape following established procedures. The presence of the drugs was then confirmed by direct analysis on the tape without further processing using SALDI- or MALDI-TOF-MS. The black magnetic fingerprint powder provided visual enhancement of the CNA-fingermark while no visual enhancement was observed for marks dusted with DHB powder. Similar [M + H](+) peaks for all the drug analytes were observed for both methods along with some sodium and potassium adducts for SALDI-MS and some major fragment ions but the SALDI signals were generally more intense. Simple exposure to acetone vapour of the CNA-developed marks enabled their effective transfer onto the tape which was crucial for subsequent MS detection of the analytes.

  3. Functionalization of silicon nanowire arrays by silver nanoparticles for the laser desorption ionization mass spectrometry analysis of vegetable oils.

    PubMed

    Picca, Rosaria Anna; Calvano, Cosima Damiana; Lo Faro, Maria Josè; Fazio, Barbara; Trusso, Sebastiano; Ossi, Paolo Maria; Neri, Fortunato; D'Andrea, Cristiano; Irrera, Alessia; Cioffi, Nicola

    2016-09-01

    In this work, novel hybrid nanostructured surfaces, consisting of dense arrays of silicon nanowires (SiNWs) functionalized by Ag nanoparticles (AgNP/SiNWs), were used for the laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS) analysis of some typical unsaturated food components (e.g. squalene, oleic acid) to assess their MS performance. The synthesis of the novel platforms is an easy, cost-effective process based on the maskless wet-etching preparation at room temperature of SiNWs followed by their decoration with AgNPs, produced by pulsed laser deposition. No particular surface pretreatment or addition of organic matrixes/ionizers was necessary. Moreover, oil extracts (e.g. extra virgin olive oil, peanut oil) could be investigated on AgNP/SiNWs surfaces, revealing their different MS profiles. It was shown that such substrates operate at reduced laser energy, typically generating intense silver cluster ions and analyte adducts. A comparison with bare SiNWs was also performed, indicating the importance of AgNP density on NW surface. In this case, desorption/ionization on silicon was invoked as probable LDI mechanism. Finally, the influence of SiNW length and surface composition on MS results was assessed. The combination of typical properties of SiNWs (hydrophobicity, antireflectivity) with ionization ability of metal NPs can be a valid methodology for the further development of nanostructured surfaces in LDI-TOF MS applications. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27476797

  4. Desorption/Ionization Fluence Thresholds and Improved Mass Spectral Consistency Measured Using a Flattop Laser Profile in the Bioaerosol Mass Spectrometry of Single Bacillus Endospores

    SciTech Connect

    Steele, P T; Srivastava, A; Pitesky, M E; Fergenson, D P; Tobias, H J; Gard, E E; Frank, M

    2004-11-30

    Bioaerosol mass spectrometry (BAMS) is being developed to analyze and identify biological aerosols in real-time. Mass spectra of individual Bacillus endospores were measured here with a bipolar aerosol time-of-flight mass spectrometer in which molecular desorption and ionization were produced using a single laser pulse from a Q-switched, frequency-quadrupled Nd:YAG laser that was modified to have an approximately flattop profile. The flattened laser profile allowed the minimum fluence required to desorb and ionize significant numbers of ions from single aerosol particles to be determined. For Bacillus spores this threshold had a mean value of approximately 1 nJ/{micro}m{sup 2} (0.1 J/cm{sup 2}). Thresholds for individual spores, however, could apparently deviate by 20% or more from the mean. Threshold distributions for clumps of MS2 bacteriophage and bovine serum albumin were subsequently determined. Finally, the flattened profile was observed to increase the reproducibility of single spore mass spectra. This is consistent with the general conclusions of our earlier paper on the fluence dependence of single spore mass spectra and is particularly significant because it is expected to enable more robust differentiation and identification of single bioaerosol particles.

  5. High-Spatial and High-Mass Resolution Imaging of Surface Metabolites of Arabidopsis thaliana by Laser Desorption-Ionization Mass Spectrometry Using Colloidal Silver

    SciTech Connect

    Jun, Ji Hyun; Song, Zhihong; Liu, Zhenjiu; Nikolau, Basil J.; Yeung, Edward S.; and Lee, Young Jin

    2010-03-17

    High-spatial resolution and high-mass resolution techniques are developed and adopted for the mass spectrometric imaging of epicuticular lipids on the surface of Arabidopsis thaliana. Single cell level spatial resolution of {approx}12 {micro}m was achieved by reducing the laser beam size by using an optical fiber with 25 {micro}m core diameter in a vacuum matrix-assisted laser desorption ionization-linear ion trap (vMALDI-LTQ) mass spectrometer and improved matrix application using an oscillating capillary nebulizer. Fine chemical images of a whole flower were visualized in this high spatial resolution showing substructure of an anther and single pollen grains at the stigma and anthers. The LTQ-Orbitrap with a MALDI ion source was adopted to achieve MS imaging in high mass resolution. Specifically, isobaric silver ion adducts of C29 alkane (m/z 515.3741) and C28 aldehyde (m/z 515.3377), indistinguishable in low-resolution LTQ, can now be clearly distinguished and their chemical images could be separately constructed. In the application to roots, the high spatial resolution allowed molecular MS imaging of secondary roots and the high mass resolution allowed direct identification of lipid metabolites on root surfaces.

  6. Characterization of B- and C-type low molecular weight glutenin subunits by electrospray ionization mass spectrometry and matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Muccilli, Vera; Cunsolo, Vincenzo; Saletti, Rosaria; Foti, Salvatore; Masci, Stefania; Lafiandra, Domenico

    2005-02-01

    Low molecular weight glutenin subunits (LMW-GS) are typically subdivided into three groups, according to their molecular weights and isoelectric points, namely the B-, C-, and D groups. Enriched B- and C-type LMW-GS fractions extracted from the bread wheat cultivar Chinese Spring were characterized using high performance liquid chromatography (HPLC) directly interfaced with electrospray ionization mass spectrometry and HPLC coupled off-line with matrix-assisted laser desorption/ionization mass spectrometry, in order to ascertain the number and relative molecular masses of the components present in each fraction and determine the number of cysteine residues. About 70 components were detected in each of the fractions examined by the combined use of these two techniques, with 18 components common to both fractions. Analysis of the fractions after alkylation with 4-vinylpyridine allowed determination of the number of the cysteines present in about 40 subunits. The proteins detected were tentatively classified based on the relative molecular masses and number of cysteine residues. Cross-contamination was found in both B- and C- fractions, along with the presence of D-type LMW-GS. The two fractions also contained unexpected components, probably lipid transfer proteins and omega-gliadins. The presence of extensive microheterogeneity was suggested by the detection of several co-eluting proteins with minor differences in their molecular masses.

  7. Imprint Desorption Electrospray Ionization Mass Spectrometry Imaging for Monitoring Secondary Metabolites Production during Antagonistic Interaction of Fungi.

    PubMed

    Tata, Alessandra; Perez, Consuelo; Campos, Michel L; Bayfield, Mark A; Eberlin, Marcos N; Ifa, Demian R

    2015-12-15

    Direct analysis of microbial cocultures grown on agar media by desorption electrospray ionization mass spectrometry (DESI-MS) is quite challenging. Due to the high gas pressure upon impact with the surface, the desorption mechanism does not allow direct imaging of soft or irregular surfaces. The divots in the agar, created by the high-pressure gas and spray, dramatically change the geometry of the system decreasing the intensity of the signal. In order to overcome this limitation, an imprinting step, in which the chemicals are initially transferred to flat hard surfaces, was coupled to DESI-MS and applied for the first time to fungal cocultures. Note that fungal cocultures are often disadvantageous in direct imaging mass spectrometry. Agar plates of fungi present a complex topography due to the simultaneous presence of dynamic mycelia and spores. One of the most devastating diseases of cocoa trees is caused by fungal phytopathogen Moniliophthora roreri. Strategies for pest management include the application of endophytic fungi, such as Trichoderma harzianum, that act as biocontrol agents by antagonizing M. roreri. However, the complex chemical communication underlying the basis for this phytopathogen-dependent biocontrol is still unknown. In this study, we investigated the metabolic exchange that takes place during the antagonistic interaction between M. roreri and T. harzianum. Using imprint-DESI-MS imaging we annotated the secondary metabolites released when T. harzianum and M. roreri were cultured in isolation and compared these to those produced after 3 weeks of coculture. We identified and localized four phytopathogen-dependent secondary metabolites, including T39 butenolide, harzianolide, and sorbicillinol. In order to verify the reliability of the imprint-DESI-MS imaging data and evaluate the capability of tape imprints to extract fungal metabolites while maintaining their localization, six representative plugs along the entire M. roreri/T. harzianum

  8. Detergent enhancement of on-tissue protein analysis by matrix-assisted laser desorption/ionization imaging mass spectrometry.

    PubMed

    Mainini, Veronica; Angel, Peggi M; Magni, Fulvio; Caprioli, Richard M

    2011-01-15

    Matrix-Assisted Laser Desorption/Ionization (MALDI) Imaging Mass Spectrometry (IMS) is a molecular technology that allows simultaneous investigation of the content and spatial distribution of molecules within tissue. In this work, we examine different classes of detergents, the anionic sodium dodecyl sulfate (SDS), the nonionic detergents Triton X-100, Tween 20 and Tween 80, and the zwitterionic 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate (CHAPS) for use in MALDI IMS of analytes above m/z 4000. These detergents were found to be compatible with MALDI MS and did not cause signal suppression relative to non-detergent applications and did not produce interfering background signals. In general, these detergents enhanced signal acquisition within the mass range m/z 4-40 000. Adding detergents into the matrix was comparable with the separate application of detergent and matrix. Evaluation of spectra collected from organ-specific regions of a whole mouse pup section showed that different detergents perform optimally with different organs, indicating that detergent selection should be optimized on the specific tissue for maximum gain. These data show the utility of detergents towards enhancement of protein signals for on-tissue MALDI IMS analysis.

  9. Molecular Characterization of Organic Aerosol Using Nanospray Desorption/Electrospray Ionization Mass Spectrometry: CalNex 2010 field study

    SciTech Connect

    O'Brien, Rachel E.; Laskin, Alexander; Laskin, Julia; Liu, Shang; Weber, Robin; Russell, Lynn; Goldstein, Allen H.

    2013-04-01

    Aerosol samples from the CalNex 2010 field study were analyzed using high resolution mass spectrometry (HR-MS) coupled to a nanospray-desorption/electrospray ionization (nano-DESI) source. The samples were collected in Bakersfield, CA on June 22-23, 2010. The chemical formulas of over 1300 unique molecular species were detected in the mass range of 50-800 m/z. Our analysis focused on identification of two main groups: compounds containing only carbon, hydrogen, and oxygen (CHO only), and nitrogen-containing organic compounds (NOC). The NOC accounted for 35% (by number) of the compounds observed in the afternoon, and for 59% in the early morning samples. By comparing plausible reactant-product pairs, we propose that over 50% of the NOC in each sample could have been formed through reactions transforming carbonyls into imines. The CHO only compounds were dominant in the afternoon suggesting a photochemical source. The average O:C ratios of all observed compounds were fairly consistent throughout the day, ranging from 0.34 in the early morning to 0.37 at night. We conclude that both photooxidation and ammonia chemistry play important roles in forming the compounds observed in this mixed urban-rural environment.

  10. Quantitative mass spectrometry imaging of emtricitabine in cervical tissue model using infrared matrix-assisted laser desorption electrospray ionization

    PubMed Central

    Bokhart, Mark T.; Rosen, Elias; Thompson, Corbin; Sykes, Craig; Kashuba, Angela D. M.; Muddiman, David C.

    2015-01-01

    A quantitative mass spectrometry imaging (QMSI) technique using infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) is demonstrated for the antiretroviral (ARV) drug emtricitabine in incubated human cervical tissue. Method development of the QMSI technique leads to a gain in sensitivity and removal of interferences for several ARV drugs. Analyte response was significantly improved by a detailed evaluation of several cationization agents. Increased sensitivity and removal of an isobaric interference was demonstrated with sodium chloride in the electrospray solvent. Voxel-to-voxel variability was improved for the MSI experiments by normalizing analyte abundance to a uniformly applied compound with similar characteristics to the drug of interest. Finally, emtricitabine was quantified in tissue with a calibration curve generated from the stable isotope-labeled analog of emtricitabine followed by cross-validation using liquid chromatography tandem mass spectrometry (LC-MS/MS). The quantitative IR-MALDESI analysis proved to be reproducible with an emtricitabine concentration of 17.2±1.8 μg/gtissue. This amount corresponds to the detection of 7 fmol/voxel in the IR-MALDESI QMSI experiment. Adjacent tissue slices were analyzed using LC-MS/MS which resulted in an emtricitabine concentration of 28.4±2.8 μg/gtissue. PMID:25318460

  11. Rapid assignment of malting barley varieties by matrix-assisted laser desorption-ionisation - Time-of-flight mass spectrometry.

    PubMed

    Šedo, Ondrej; Kořán, Michal; Jakešová, Michaela; Mikulíková, Renata; Boháč, Michal; Zdráhal, Zbyněk

    2016-09-01

    A method for discriminating malting barley varieties based on direct matrix-assisted laser desorption-ionisation - time-of-flight mass spectrometry (MALDI-TOF MS) fingerprinting of proteins was developed. Signals corresponding to hordeins were obtained by simple mixing of powdered barley grain with a MALDI matrix solution containing 12.5mgmL(-1) of ferulic acid in an acetonitrile:water:formic acid 50:33:17 v/v/v mixture. Compared to previous attempts at MALDI-TOF mass spectrometric analysis of barley proteins, the extraction and fractionation steps were practically omitted, resulting in a significant reduction in analytical time and costs. The discriminatory power was examined on twenty malting barley varieties and the practicability of the method was tested on sixty barley samples acquired from Pilsner Urquell Brewery. The method is proposed as a rapid tool for variety assignment and purity determination of malting barley that may replace gel electrophoresis currently used for this purpose. PMID:27041307

  12. Evaluation of Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry for Second-Generation Lignin Analysis

    PubMed Central

    Richel, Aurore; Vanderghem, Caroline; Simon, Mathilde; Wathelet, Bernard; Paquot, Michel

    2012-01-01

    Matrix-Assisted Laser Desorption/Ionization time-of-flight (MALDI-TOF) mass spectrometry is evaluated as an elucidation tool for structural features and molecular weights estimation of some extracted herbaceous lignins. Optimization of analysis conditions, using a typical organic matrix, namely α-cyano-4-hydroxycinnamic acid (CHCA), in combination with α-cyclodextrin, allows efficient ionization of poorly soluble lignin materials and suppression of matrix-related ions background. Analysis of low-mass fragments ions (m/z 100–600) in the positive ion mode offers a “fingerprint” of starting lignins that could be a fine strategy to qualitatively identify principal inter-unit linkages between phenylpropanoid units. The molecular weights of lignins are estimated using size exclusion chromatography and compared to MALDI-TOF-MS profiles. Miscanthus (Miscanthus x giganteus) and Switchgrass (Panicum Virgatum L.) lignins, recovered after a formic acid/acetic acid/water process or aqueous ammonia soaking, are selected as benchmarks for this study. PMID:23300342

  13. Inflation-Fixation Method for Lipidomic Mapping of Lung Biopsies by Matrix Assisted Laser Desorption/Ionization-Mass Spectrometry Imaging.

    PubMed

    Carter, Claire L; Jones, Jace W; Farese, Ann M; MacVittie, Thomas J; Kane, Maureen A

    2016-05-01

    Chronic respiratory diseases are among the leading causes of deaths worldwide and major contributors of morbidity and global disease burden. To appropriately investigate lung disease, the respiratory airways must be fixed in their physiological orientation and should be inflated prior to investigations. We present an inflation-fixation method that enables lipidomic investigations of whole lung samples and resected biopsy specimens by matrix-assisted laser desorption/ionization-mass spectrometry imaging (MALDI-MSI). Formalin-inflation enables sample preparation to parallel standard clinical and surgical procedures, in addition to greatly reducing the complexity of analysis, by decreasing the number of analytes in the MALDI plume and reducing adduct formation in the resulting mass spectra. The reduced complexity increased sensitivity and enabled high-resolution imaging acquisitions without any loss in analyte detection at 10 and 20 μm scans. We present a detailed study of over 100 lipid ions detected in positive and negative ion modes covering the conducting and respiratory airways and parts of the peripheral nervous tissue running through the lungs. By defining the resolution required for clear definition of the alveolar space and thus the respiratory airways we have provided a guideline for MSI investigations of respiratory diseases involving the airways, including the interstitium. This study has provided a detailed map of lipid species and their localization within larger mammalian lung samples, for the first time, thus categorizing the lipidome for future MALDI-MSI studies of pulmonary diseases. PMID:27028398

  14. Evaluation of matrix-assisted laser desorption/ionization mass spectrometry for second-generation lignin analysis.

    PubMed

    Richel, Aurore; Vanderghem, Caroline; Simon, Mathilde; Wathelet, Bernard; Paquot, Michel

    2012-01-01

    Matrix-Assisted Laser Desorption/Ionization time-of-flight (MALDI-TOF) mass spectrometry is evaluated as an elucidation tool for structural features and molecular weights estimation of some extracted herbaceous lignins. Optimization of analysis conditions, using a typical organic matrix, namely α-cyano-4-hydroxycinnamic acid (CHCA), in combination with α-cyclodextrin, allows efficient ionization of poorly soluble lignin materials and suppression of matrix-related ions background. Analysis of low-mass fragments ions (m/z 100-600) in the positive ion mode offers a "fingerprint" of starting lignins that could be a fine strategy to qualitatively identify principal inter-unit linkages between phenylpropanoid units. The molecular weights of lignins are estimated using size exclusion chromatography and compared to MALDI-TOF-MS profiles. Miscanthus (Miscanthus x giganteus) and Switchgrass (Panicum Virgatum L.) lignins, recovered after a formic acid/acetic acid/water process or aqueous ammonia soaking, are selected as benchmarks for this study.

  15. Imaging of a tribolayer formed from ionic liquids by laser desorption/ionization-reflectron time-of-flight mass spectrometry.

    PubMed

    Gabler, Christoph; Pittenauer, Ernst; Dörr, Nicole; Allmaier, Günter

    2012-12-18

    For the first time, imaging using laser desorption/ionization (LDI) reflectron time-of-flight (RTOF) mass spectrometry (MS) was demonstrated to be a powerful tool for an offline monitoring of tribometrical experiments directly from disc specimen applying selected ammonium-, phosphonium-, and sulfonium-based ionic liquids (IL) with bis(trifluoromethylsulfonyl)imide as counterion for lubrication. The direct measurement of IL tribolayers by LDI-MS allowed the visualization of the lubricants in the form of the distribution of their intact cations and the anion in and outside the wear scar after the tribometrical experiment with a low degree of in-source generated fragmentation. Besides, also, an oxidation product formed during a tribometrical experiment was detected and located exclusively in the wear track. Comparative data of identical wear tracks were obtained by X-ray photoelectron spectroscopy (XPS) imaging not only enabling the determination of elemental distributions of the IL across the area imaged but also corroborating the mass spectrometry imaging (MSI) data, thus generating multimodal images. Merging data from MSI and XPS imaging exhibited that areas, where iron-fluorine bonds were detected in the wear track, are corresponding to data from LDI-MS imaging showing absence of IL cations and anions.

  16. Chemical characterization of crude petroleum using nanospray desorption electrospray ionization coupled with high-resolution mass spectrometry.

    PubMed

    Eckert, Peter A; Roach, Patrick J; Laskin, Alexander; Laskin, Julia

    2012-02-01

    Nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was used for the first time for the analysis of the polar constituents of liquid petroleum crude oil samples. The analysis was performed in both positive and negative ionization modes using three solvents, one of which (acetonitrile/toluene mixture) is commonly used in petroleomics studies while two other polar solvents (acetonitrile/water and methanol/water mixtures) are generally not compatible with petroleum characterization using mass spectrometry. The results demonstrate that nano-DESI analysis efficiently ionizes petroleum constituents soluble in a particular solvent. When acetonitrile/toluene is used as a solvent, nano-DESI generates electrospray-like spectra. In contrast, strikingly different spectra were obtained using acetonitrile/water and methanol/water. Comparison with the literature data indicates that these solvents selectively extract water-soluble constituents of the crude oil. Water-soluble compounds are predominantly observed as sodium adducts in nano-DESI spectra indicating that addition of sodium to the solvent may be a viable approach for efficient ionization of water-soluble crude oil constituents. Nano-DESI enables rapid screening of different classes of compounds in crude oil samples based on their solubility in solvents that are rarely used for petroleum characterization providing better coverage of the crude oil composition as compared to electrospray ionization (ESI). It also enables rapid characterization of water-soluble components of petroleum samples that is difficult to perform using traditional approaches.

  17. Quantitative mass spectrometry imaging of emtricitabine in cervical tissue model using infrared matrix-assisted laser desorption electrospray ionization.

    PubMed

    Bokhart, Mark T; Rosen, Elias; Thompson, Corbin; Sykes, Craig; Kashuba, Angela D M; Muddiman, David C

    2015-03-01

    A quantitative mass spectrometry imaging (QMSI) technique using infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) is demonstrated for the antiretroviral (ARV) drug emtricitabine in incubated human cervical tissue. Method development of the QMSI technique leads to a gain in sensitivity and removal of interferences for several ARV drugs. Analyte response was significantly improved by a detailed evaluation of several cationization agents. Increased sensitivity and removal of an isobaric interference was demonstrated with sodium chloride in the electrospray solvent. Voxel-to-voxel variability was improved for the MSI experiments by normalizing analyte abundance to a uniformly applied compound with similar characteristics to the drug of interest. Finally, emtricitabine was quantified in tissue with a calibration curve generated from the stable isotope-labeled analog of emtricitabine followed by cross-validation using liquid chromatography tandem mass spectrometry (LC-MS/MS). The quantitative IR-MALDESI analysis proved to be reproducible with an emtricitabine concentration of 17.2 ± 1.8 μg/gtissue. This amount corresponds to the detection of 7 fmol/voxel in the IR-MALDESI QMSI experiment. Adjacent tissue slices were analyzed using LC-MS/MS which resulted in an emtricitabine concentration of 28.4 ± 2.8 μg/gtissue.

  18. Analysis of Microbial Mixtures by Matrix-assisted Laser Desorption/Ionization time-of-flight Mass Spectrometry

    SciTech Connect

    Wahl, Karen L.; Wunschel, Sharon C.; Jarman, Kristin H.; Valentine, Nancy B.; Petersen, Catherine E.; Kingsley, Mark T.; Zartolas, Kimberly A.; Saenz, Adam J.

    2002-12-15

    Many different laboratories are currently developing mass-spectrometric techniques to analyze and identify microorganisms. However, minimal work has been done with mixtures of bacteria. To demonstrate that microbial mixtures could be analyzed by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), mixed bacterial cultures were analyzed in a double-blind fashion. Nine different bacterial species currently in our MALDI-MS fingerprint library were used to generate 50 different simulated mixed bacterial cultures similar to that done for an initial blind study previously reported.(1) The samples were analyzed by MALDI-MS with automated data extraction and analysis algorithms developed in our laboratory. The components present in the sample were identified correctly to the species level in all but one of the samples. However, correctly eliminating closely related organisms was challenging for the current algorithms, especially in differentiating Serratia marcescens, Escherichia coli, and Yersinia enterocolitica, which have some similarities in their MALDI-MS fingerprints. Efforts to improve the specificity of the algorithms are in progress.

  19. Thin-layer chromatography and mass spectrometry coupled using proximal probe thermal desorption with electrospray or atmospheric pressure chemica lionization

    SciTech Connect

    Ovchinnikova, Olga S; Van Berkel, Gary J

    2010-01-01

    An atmospheric pressure proximal probe thermal desorption sampling method coupled with secondary ionization by electrospray or atmospheric pressure chemical ionization was demonstrated for the mass spectrometric analysis of a diverse set of compounds (dyestuffs, pharmaceuticals, explosives and pesticides) separated on various high-performance thin-layer chromatography plates. Line scans along or through development lanes on the plates were carried out by moving the plate relative to a stationary heated probe positioned close to or just touching the stationary phase surface. Vapors of the compounds thermally desorbed from the surface were drawn into the ionization region of a combined electrospray ionization/atmospheric pressure chemical ionization source where they merged with reagent ions and/or charged droplets from a corona discharge or an electrospray emitter and were ionized. The ionized components were then drawn through the atmospheric pressure sampling orifice into the vacuum region of a triple quadrupole mass spectrometer and detected using full scan, single ion monitoring, or selected reaction monitoring mode. Studies of variable parameters and performance metrics including the proximal probe temperature, gas flow rate into the ionization region, surface scan speed, read-out resolution, detection limits, and surface type are discussed.

  20. Ambient desorption/ionization mass spectrometry using a liquid sampling-atmospheric glow discharge (LS-APGD) ionization source.

    PubMed

    Marcus, R Kenneth; Burdette, Carolyn Q; Manard, Benjamin T; Zhang, Lynn X

    2013-10-01

    A novel approach to ambient desorption/ionization mass spectrometry (ADI-MS) is described, based on a recently developed liquid sampling-atmospheric pressure glow discharge (LS-APGD) ionization source. The device is essentially unmodified relative to its implementation in elemental mass spectrometry, where the operational space is characterized by low operation power (<10 W) and low solution delivery rates (<50 μL min(-1)). In this implementation, the plasma is produced between a Ni anode and an electrolytic liquid (1 M HNO3) cathode flowing through a glass capillary that is angled towards the sample surface, at a distance of ~2 mm away. Analyte species can be desorbed/ionized from neat solution residues and complex solid samples. The ADI-LS-APGD source is mounted onto the source interface of a Thermo Finnigan LCQ Advantage Max quadrupole ion trap mass spectrometer without modifications to the instrument faceplate or ion optics. Described here is the initial evaluation of the roles of source geometry and working parameters, including electrolytic solution composition and plasma current, on the response of caffeine residues, with preliminary limits of detection based on the relative standard deviation of the spectral background suggested to be on the 10-pg level. Demonstrative spectra are presented for green tea extracts and raw leaves, coffee beans, a dried (raw) tobacco leaf, an analgesic tablet, and paper currency. Versatility is further revealed through the determination of components in common cigarette smoke. In each case, the spectra are characterized by (M + H)(+) species of the expected constituents. The capacity for a single source to perform both in solution and particulate elemental analysis (as shown previously) and ADI of molecular species is unique in the realm of mass spectrometry.

  1. Probing Molecular Composition of Soil Organic Matter with Nanospray Desorption Electrospray Ionization (nano-DESI) High-Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Laskin, A.; Laskin, J.; Nizkorodov, S.

    2014-12-01

    The standard techniques for chemical analysis of SOM often lack molecular detail necessary for characterization of the key classes of compounds in soil necessary for the development of predictive models. High-resolution mass spectrometry (HR-MS) combined with tandem mass spectrometry (MSn) is the technique of choice for structural characterization of individual molecules in complex environmental mixtures because HR-MS enables chemical characterization of complex samples with a level of detail that is not attainable using other techniques. However, the power of this technique for characterization of SOM has been demonstrated only recently. Nanospray desorption ionization (nano-DESI) bypasses the traditional SOM extraction steps and provides the unique ability to record SOM mass spectra from small whole-soil samples. Nano-DESI benefits from a short sample preparation time (dozens of samples can be analyzed in a matter of hours by simply swapping the samples on the sample holder and running a pre-programmed positioning stage protocol), fast analysis time (useful signal results from only a few seconds of contact between the sample and the liquid bridge), and highly sensitive detection (less than 10 ng of organic mass is required for analysis). The nano-DESI method is minimally destructive. Only a small spot (typically < 1mm) is in contact with the solvent bridge during the analysis, and the rest of the sample is unaffected. Sampling over multiple spots on the same sample in effect replaces the need to extract a large amount of SOM from a soil sample in order to homogenize it, as done in conventional soil analysis. Another critical advantage of nano-DESI is that it makes it possible to observe organic components that cannot be easily detected using traditional ESI method (69). Specifically, by minimizing the residence time of analyte in the spray solvent, it enables detection and structural characterization of chemically labile molecules in environmental samples, which

  2. Interlaboratory Comparison of Intact-Cell Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry Results for Identification and Differentiation of Brucella spp.

    PubMed Central

    Karger, Axel; Melzer, Falk; Timke, Markus; Bettin, Barbara; Kostrzewa, Markus; Nöckler, Karsten; Hohmann, Angelika; Tomaso, Herbert; Neubauer, Heinrich

    2013-01-01

    Classical microbiological diagnosis of human brucellosis is time-consuming, hazardous, and subject to variable interpretation. Intact-cell matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) was evaluated for the routine identification of Brucella spp. Analysis of mass peak patterns allowed accurate identification to the genus level. However, statistical models based on peak intensities were needed for definite species differentiation. Interlaboratory comparison confirmed the reproducibility of the results. PMID:23850950

  3. A mass spectrometric system for analyzing thermal desorption spectra of ion-implanted argon and cesium in tungsten. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Wood, G. M., Jr.

    1974-01-01

    A mass spectrometric system for determining the characteristics of materials used in instrumental development and aerospace applications was developed. The desorption spectra of cesium that was ion-implanted into polycrystalline tungsten and the effects on the spectra of bombardment of the tungsten by low energy (70 eV) electrons were investigated. Work function changes were measured by the retarding potential diode method. Flash desorption characteristics were observed and gas-reaction mechanisms of the surface of heated metal filaments were studied. Desorption spectra were measured by linearly increasing the sample temperature at a selected rate, the temperature cycling being generated from a ramp-driven dc power supply, with the mass spectrometer tuned to a mass number of interest. Results of the study indicate an anomolous desorption mechanism following an electron bombardment of the sample surface. The enhanced spectra are a function of the post-bombardment time and energy and are suggestive of an increased concentration of cesium atoms, up to 10 or more angstroms below the surface.

  4. Histology-Guided High-Resolution Matrix-Assisted Laser Desorption Ionization Mass Spectrometry Imaging.

    PubMed

    Heijs, Bram; Abdelmoula, Walid M; Lou, Sha; Briaire-de Bruijn, Inge H; Dijkstra, Jouke; Bovée, Judith V M G; McDonnell, Liam A

    2015-12-15

    Mass spectrometry imaging (MSI) is widely used for clinical research because when combined with histopathological analysis the molecular signatures of specific cells/regions can be extracted from the often-complex histologies of pathological tissues. The ability of MSI to stratify patients according to disease, prognosis, and response is directly attributable to this cellular specificity. MSI developments are increasingly focused on further improving specificity, through higher spatial resolution to better localize the signals or higher mass resolution to better resolve molecular ions. Higher spatial/mass resolution leads to increased data size and longer data acquisition times. For clinical applications, which analyze large series of patient tissues, this poses a challenge to keep data load and acquisition time manageable. Here we report a new tool to perform histology guided MSI; instead of analyzing large parts of each tissue section the histology from adjacent tissue sections is used to focus the analysis on the areas of interest, e.g., comparable cell types in different patient tissues, thereby minimizing data acquisition time and data load. The histology tissue section is annotated and then automatically registered to the MSI-prepared tissue section; the registration transformation is then applied to the annotations, enabling them to be used to define the MSI measurement regions. Using a series of formalin-fixed, paraffin-embedded human myxoid liposarcoma tissues, we demonstrate an 80% reduction of data load and acquisition time, thereby enabling high resolution (mass or spatial) to be more readily applied to clinical research. The software is freely available for download. PMID:26595321

  5. Fuzzy Logic Classification of Imaging Laser Desorption Fourier Transform Mass Spectrometry Data

    SciTech Connect

    Timothy R. McJunkin; Jill R. Scott

    2008-06-01

    The fuzzy logic method is applied to classification of mass spectra obtained with an imaging internal source Fourier transform mass spectrometer (I2LD-FTMS). Traditionally, an operator uses the relative abundance of ions with specific mass-to-charge (m/z) ratios to categorize spectra. An operator does this by comparing the spectrum of m/z versus abundance of an unknown sample against a library of spectra from known samples. Automated positioning and acquisition allow the I2LD-FTMS to acquire data from very large grids, which would require classification of up to 3600 spectra per hour to keep pace with the acquisition. The tedious job of classifying numerous spectra generated in an I2LD-FTMS imaging application can be replaced by a fuzzy rule base if the cues an operator uses can be encapsulated. Appropriate methods for assigning fuzzy membership values for inputs (e.g., mass spectrum abundances) and choice of fuzzy inference operators to translate linguistic antecedent into confidence values for the consequence (or in this case the classification) is followed by using the maximum confidence and a necessary minimum threshold for making a crisp decision. This paper also describes a method for gathering statistics on ions, which are not currently used in the rule base, but which may be candidates for making the rule base more accurate and complete or to form new rule bases based on data obtained from known samples. A spatial method for classifying spectra with low membership values, based on neighboring sample classifications, is also presented.

  6. Thermal desorption single particle mass spectrometry of ambient aerosol in Shanghai

    NASA Astrophysics Data System (ADS)

    Zhai, Jinghao; Wang, Xinning; Li, Jingyan; Xu, Tingting; Chen, Hong; Yang, Xin; Chen, Jianmin

    2015-12-01

    Submicron aerosol volatility, chemical composition, and mixing state were simultaneously measured using a thermodenuder (TD) in-line with a single particle aerosol mass spectrometry (SPAMS) during Nov.12 to Dec. 11 of 2014 in Shanghai. By heating up to 250 °C, the signals of refractory species such as elemental carbon, metallic compounds, and mineral dust in aerosols were enhanced in the mass spectra. At 250 °C, the main particle types present in the size range of 0.2-1.0 μm were biomass burning (37% by number) and elemental carbon (20%). From 1.0 to 2.0 μm, biomass burning (30%), dust (19%) and metal-rich (18%) were the primary particle types. CN- signal remained in the mass spectra of the heated biomass burning particles suggests the existence of some extremely low-volatility nitrogen-containing organics. Laboratory experiments were conducted by burning rice straws, the main source material of biomass burning particles in Southern China, to confirm the less volatile composition contributed by biomass burning. Strong CN- with relative area >0.21 was observed in most of the laboratory-made biomass burning particles when heated above 200 °C and was selected as a new marker to identify the biomass burning particles in the field. The TD-SPAMS measured the size-resolved chemical composition of the individual particle residues at different temperatures and offered more information on the aging processes of primary particles and their sources.

  7. Non-proximate detection of small and large molecules by desorption electrospray ionization and desorption atmospheric pressure chemical ionization mass spectrometry: instrumentation and applications in forensics, chemistry, and biology.

    PubMed

    Cotte-Rodríguez, Ismael; Mulligan, Christopher C; Cooks, R Graham

    2007-09-15

    Ambient surfaces are examined by mass spectrometry at distances of up to 3 m from the instrument without any prior sample preparation. Non-proximate versions of the desorption electrospray ionization (DESI) and desorption atmospheric pressure chemical ionization experiments are shown to allow rapid, sensitive, and selective detection of trace amounts of active ingredients in pharmaceutical drug formulations, illicit drugs (methamphetamine, cocaine, and diacetylmorphine), organic salts, peptides, chemical warfare agent simulants, and other small organic compounds. Utilizing an ion transport tube to transport analyte ions to the mass spectrometer, nonproximate DESI allows one to collect high-quality, largely interference-free spectra with signal-to-noise (S/N) ratios of more than 100. High selectivity is achieved by tandem mass spectrometry and by reactive DESI, a variant experiment in which reagents added into the solvent spray allow bond-forming reactions with the analyte. Ion/molecule reactions were found to selectively suppress the response of mixture components other than the analyte of interest in nonproximate-DESI. Flexible ion transport tubing is also investigated, allowing performance similar to stainless steel tubing in the transport of ions from the sample to the mass spectrometer. Transfer tube temperature effects are examined. A multiple sprayer DESI source capable of analyzing a larger sample area was evaluated to decrease the sampling time and increase sample throughput. Low nanogram detection limits were obtained for the compounds studied from a wide variety of surfaces, even those present in complex matrixes.

  8. Study of kinetic desorption rate constant in fish muscle and agarose gel model using solid phase microextraction coupled with liquid chromatography with tandem mass spectrometry.

    PubMed

    Togunde, Oluranti Paul; Oakes, Ken; Servos, Mark; Pawliszyn, Janusz

    2012-09-12

    This study aims to use solid phase microextraction (SPME), a simple tool to investigate diffusion rate (time) constant of selected pharmaceuticals in gel and fish muscle by comparing desorption rate of diffusion of the drugs in both agarose gel prepared with phosphate-buffered saline (PBS; pH 7.4) and fish muscle. The gel concentration (agarose gel model) that could be used to simulate tissue matrix (fish muscle) for free diffusion of drugs under in vitro and in vivo conditions was determined to model mass transfer phenomena between fibre polymer coating and environmental matrix such that partition coefficients and desorption time constant (diffusion coefficient) can be determined. SPME procedure involves preloading the extraction phase (fibre) with the standards from spiked PBS for 1h via direct extraction. Subsequently, the preloaded fibre is introduced to the sample such fish or agarose gel for specified time ranging from 0.5 to 60 h. Then, fibre is removed at specified time and desorbed in 100 μL of desorption solution (acetonitrile: water 1:1) for 90 min under agitation speed of 1000 rpm. The samples extract were immediately injected to the instrument and analysed using liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). The limit of detection of the method in gel and fish muscle was 0.01-0.07 ng mL(-1) and 0.07-0.34 ng g(-1), respectively, while the limit quantification was 0.10-0.20 ng mL(-1) in gel samples and 0.40-0.97 ng g(-1) in fish sample. The reproducibility of the method was good (5-15% RSD). The results suggest that kinetics of desorption of the compounds in fish tissue and different viscosity of gel can be determined using desorption time constant. In this study, desorption time constant which is directly related to desorption rate (diffusion kinetics) of selected drugs from the fibre to the gel matrix is faster as the viscosity of the gel matrix reduces from 2% (w/v) to 0.8% (w/v). As the concentration of gel reduces

  9. Identification of dermatophytes by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    de Respinis, Sophie; Tonolla, Mauro; Pranghofer, Sigrid; Petrini, Liliane; Petrini, Orlando; Bosshard, Philipp P

    2013-07-01

    In this study we evaluated the suitability of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) for the identification of dermatophytes in diagnostic laboratories. First, a spectral database was built with 108 reference strains belonging to 18 species of the anamorphic genera Epidermophyton, Microsporum and Trichophyton. All strains were well characterized by morphological criteria and ITS sequencing (gold standard). The dendrogram resulting from MALDI-TOF mass spectra was almost identical with the phylogenetic tree based on ITS sequencing. Subsequently, MALDI-TOF MS SuperSpectra were created for the identification of Epidermophyton floccosum, Microsporium audouinii, M. canis, M. gypseum (teleomorph: Arthroderma gypseum), M. gypseum (teleomorph: A. incurvatum), M. persicolor, A. benhamiae (Tax. Entity 3 and Am-Eur. race), T. erinacei, T. interdigitale (anthropophilic and zoophilic populations), T. rubrum/T. violaceum, T. tonsurans and T. terrestre. Because T. rubrum and T. violaceum did not present enough mismatches, a SuperSpectrum covering both species was created, and differentiation between them was done by comparison of eight specific peptide masses. In the second part of this study, MALDI-TOF MS with the newly created SuperSpectra was tested using 141 clinical isolates representing nine species. Analyses were done with 3-day-old cultures. Results were compared to morphological identification and ITS sequencing; 135/141 (95.8%) strains were correctly identified by MALDI-TOF MS compared to 128/141 (90.8%) by morphology. Therefore, MALDI-TOF MS has proven to be a useful and rapid identification method for dermatophytes. PMID:23228046

  10. Large-Scale Metabolite Analysis of Standards and Human Serum by Laser Desorption Ionization Mass Spectrometry from Silicon Nanopost Arrays.

    PubMed

    Korte, Andrew R; Stopka, Sylwia A; Morris, Nicholas; Razunguzwa, Trust; Vertes, Akos

    2016-09-20

    The unique challenges presented by metabolomics have driven the development of new mass spectrometry (MS)-based techniques for small molecule analysis. We have previously demonstrated silicon nanopost arrays (NAPA) to be an effective substrate for laser desorption ionization (LDI) of small molecules for MS. However, the utility of NAPA-LDI-MS for a wide range of metabolite classes has not been investigated. Here we apply NAPA-LDI-MS to the large-scale acquisition of high-resolution mass spectra and tandem mass spectra from a collection of metabolite standards covering a range of compound classes including amino acids, nucleotides, carbohydrates, xenobiotics, lipids, and other classes. In untargeted analysis of metabolite standard mixtures, detection was achieved for 374 compounds and useful MS/MS spectra were obtained for 287 compounds, without individual optimization of ionization or fragmentation conditions. Metabolite detection was evaluated in the context of 31 metabolic pathways, and NAPA-LDI-MS was found to provide detection for 63% of investigated pathway metabolites. Individual, targeted analysis of the 20 common amino acids provided detection of 100% of the investigated compounds, demonstrating that improved coverage is possible through optimization and targeting of individual analytes or analyte classes. In direct analysis of aqueous and organic extracts from human serum samples, spectral features were assigned to a total of 108 small metabolites and lipids. Glucose and amino acids were quantitated within their physiological concentration ranges. The broad coverage demonstrated by this large-scale screening experiment opens the door for use of NAPA-LDI-MS in numerous metabolite analysis applications.

  11. A simple protocol for combinatorial cyclic depsipeptide libraries sequencing by matrix-assisted laser desorption/ionisation mass spectrometry.

    PubMed

    Gurevich-Messina, Juan M; Giudicessi, Silvana L; Martínez-Ceron, María C; Acosta, Gerardo; Erra-Balsells, Rosa; Cascone, Osvaldo; Albericio, Fernando; Camperi, Silvia A

    2015-01-01

    Short cyclic peptides have a great interest in therapeutic, diagnostic and affinity chromatography applications. The screening of 'one-bead-one-peptide' combinatorial libraries combined with mass spectrometry (MS) is an excellent tool to find peptides with affinity for any target protein. The fragmentation patterns of cyclic peptides are quite more complex than those of their linear counterparts, and the elucidation of the resulting tandem mass spectra is rather more difficult. Here, we propose a simple protocol for combinatorial cyclic libraries synthesis and ring opening before MS analysis. In this strategy, 4-hydroxymethylbenzoic acid, which forms a benzyl ester with the first amino acid, was used as the linker. A glycolamidic ester group was incorporated after the combinatorial positions by adding glycolic acid. The library synthesis protocol consisted in the following: (i) incorporation of Fmoc-Asp[2-phenylisopropyl (OPp)]-OH to Ala-Gly-oxymethylbenzamide-ChemMatrix, (ii) synthesis of the combinatorial library, (iii) assembly of a glycolic acid, (iv) couple of an Ala residue in the N-terminal, (v) removal of OPp, (vi) peptide cyclisation through side chain Asp and N-Ala amino terminus and (vii) removal of side chain protecting groups. In order to simultaneously open the ring and release each peptide, benzyl and glycolamidic esters were cleaved with ammonia. Peptide sequences could be deduced from the tandem mass spectra of each single bead evaluated. The strategy herein proposed is suitable for the preparation of one-bead-one-cyclic depsipeptide libraries that can be easily open for its sequencing by matrix-assisted laser desorption/ionisation MS. It employs techniques and reagents frequently used in a broad range of laboratories without special expertise in organic synthesis.

  12. The quantitative surface analysis of an antioxidant additive in a lubricant oil matrix by desorption electrospray ionization mass spectrometry

    PubMed Central

    Da Costa, Caitlyn; Reynolds, James C; Whitmarsh, Samuel; Lynch, Tom; Creaser, Colin S

    2013-01-01

    RATIONALE Chemical additives are incorporated into commercial lubricant oils to modify the physical and chemical properties of the lubricant. The quantitative analysis of additives in oil-based lubricants deposited on a surface without extraction of the sample from the surface presents a challenge. The potential of desorption electrospray ionization mass spectrometry (DESI-MS) for the quantitative surface analysis of an oil additive in a complex oil lubricant matrix without sample extraction has been evaluated. METHODS The quantitative surface analysis of the antioxidant additive octyl (4-hydroxy-3,5-di-tert-butylphenyl)propionate in an oil lubricant matrix was carried out by DESI-MS in the presence of 2-(pentyloxy)ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as an internal standard. A quadrupole/time-of-flight mass spectrometer fitted with an in-house modified ion source enabling non-proximal DESI-MS was used for the analyses. RESULTS An eight-point calibration curve ranging from 1 to 80 µg/spot of octyl (4-hydroxy-3,5-di-tert-butylphenyl)propionate in an oil lubricant matrix and in the presence of the internal standard was used to determine the quantitative response of the DESI-MS method. The sensitivity and repeatability of the technique were assessed by conducting replicate analyses at each concentration. The limit of detection was determined to be 11 ng/mm2 additive on spot with relative standard deviations in the range 3–14%. CONCLUSIONS The application of DESI-MS to the direct, quantitative surface analysis of a commercial lubricant additive in a native oil lubricant matrix is demonstrated. © 2013 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons, Ltd. PMID:24097398

  13. Matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry applied to virus identification

    PubMed Central

    Calderaro, Adriana; Arcangeletti, Maria-Cristina; Rodighiero, Isabella; Buttrini, Mirko; Gorrini, Chiara; Motta, Federica; Germini, Diego; Medici, Maria-Cristina; Chezzi, Carlo; De Conto, Flora

    2014-01-01

    Virus detection and/or identification traditionally rely on methods based on cell culture, electron microscopy and antigen or nucleic acid detection. These techniques are good, but often expensive and/or time-consuming; furthermore, they not always lead to virus identification at the species and/or type level. In this study, Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) was tested as an innovative tool to identify human polioviruses and to identify specific viral protein biomarkers in infected cells. The results revealed MALDI-TOF MS to be an effective and inexpensive tool for the identification of the three poliovirus serotypes. The method was firstly applied to Sabin reference strains, and then to isolates from different clinical samples, highlighting its value as a time-saving, sensitive and specific technique when compared to the gold standard neutralization assay and casting new light on its possible application to virus detection and/or identification. PMID:25354905

  14. Desorption electrospray ionization imaging mass spectrometry as a tool for investigating model prebiotic reactions on mineral surfaces.

    PubMed

    Bennett, Rachel V; Cleaves, H James; Davis, Jeffrey M; Sokolov, Denis A; Orlando, Thomas M; Bada, Jeffrey L; Fernández, Facundo M

    2013-02-01

    Mineral-assisted thermal decomposition of formamide (HCONH(2)) is a heavily studied model prebiotic reaction that has offered valuable insights into the plausible pathways leading to the chemical building blocks of primordial informational polymers. To date, most efforts have focused on the analysis of formamide reaction products released in solution, although several studies have examined the role of mineral catalysts in promoting this chemistry. We show here that the direct investigation of reactive mineral surfaces by desorption electrospray ionization-mass spectrometry imaging (DESI-MSI) gives a new perspective on the important role of the mineral surface in the formation of reaction products. As a proof-of-principle example, we show that DESI-MSI allows interrogation of the molecular products produced on heterogeneous granite samples with minimal sample preparation. Purine and pyrimidine nucleobases and their derivatives are successfully detected by DESI-MSI, with a strong correlation of the spatial product distribution with the mineral microenvironment. To our knowledge, this study is the first application of DESI-MSI to the study of complex and porous mineral surfaces and their roles in chemical evolution. This DESI-MSI approach is generally applicable to a wide range of reactions or other processes involving minerals. PMID:23286321

  15. Desorption electrospray ionization imaging mass spectrometry as a tool for investigating model prebiotic reactions on mineral surfaces.

    PubMed

    Bennett, Rachel V; Cleaves, H James; Davis, Jeffrey M; Sokolov, Denis A; Orlando, Thomas M; Bada, Jeffrey L; Fernández, Facundo M

    2013-02-01

    Mineral-assisted thermal decomposition of formamide (HCONH(2)) is a heavily studied model prebiotic reaction that has offered valuable insights into the plausible pathways leading to the chemical building blocks of primordial informational polymers. To date, most efforts have focused on the analysis of formamide reaction products released in solution, although several studies have examined the role of mineral catalysts in promoting this chemistry. We show here that the direct investigation of reactive mineral surfaces by desorption electrospray ionization-mass spectrometry imaging (DESI-MSI) gives a new perspective on the important role of the mineral surface in the formation of reaction products. As a proof-of-principle example, we show that DESI-MSI allows interrogation of the molecular products produced on heterogeneous granite samples with minimal sample preparation. Purine and pyrimidine nucleobases and their derivatives are successfully detected by DESI-MSI, with a strong correlation of the spatial product distribution with the mineral microenvironment. To our knowledge, this study is the first application of DESI-MSI to the study of complex and porous mineral surfaces and their roles in chemical evolution. This DESI-MSI approach is generally applicable to a wide range of reactions or other processes involving minerals.

  16. Differentiation of Microbial Species and Strains in Coculture Biofilms by Multivariate Analysis of Laser Desorption Postionization Mass Spectra

    PubMed Central

    Bhardwaj, Chhavi; Cui, Yang; Hofstetter, Theresa; Liu, Suet Yi; Bernstein, Hans C.; Carlson, Ross P.; Ahmed, Musahid; Hanley, Luke

    2013-01-01

    7.87 to 10.5 eV vacuum ultraviolet (VUV) photon energies were used in laser desorption postionization mass spectrometry (LDPI-MS) to analyze biofilms comprised of binary cultures of interacting microorganisms. The effect of photon energy was examined using both tunable synchrotron and laser sources of VUV radiation. Principal components analysis (PCA) was applied to the MS data to differentiate species in Escherichia coli-Saccharomyces cerevisiae coculture biofilms. PCA of LDPI-MS also differentiated individual E. coli strains in a biofilm comprised of two interacting gene deletion strains, even though these strains differed from the wild type K-12 strain by no more than four gene deletions each out of approximately 2000 genes. PCA treatment of 7.87 eV LDPI-MS data separated the E. coli strains into three distinct groups, two “pure” groups, and a mixed region. Furthermore, the “pure” regions of the E. coli cocultures showed greater variance by PCA at 7.87 eV photon energies compared to 10.5 eV radiation. This is consistent with the expectation that the 7.87 eV photoionization selects a subset of low ionization energy analytes while 10.5 eV is more inclusive, detecting a wider range of analytes. These two VUV photon energies therefore give different spreads via PCA and their respective use in LDPI-MS constitute an additional experimental parameter to differentiate strains and species. PMID:24067765

  17. Molecular analysis of model gut microbiotas by imaging mass spectrometry and nano-desorption electrospray ionization reveals dietary metabolite transformations

    PubMed Central

    Rath, Christopher M.; Alexandrov, Theodore; Higginbottom, Steven K.; Song, Jiao; Milla, Marcos; Fischbach, Michael; Sonnenburg, Justin L.; Dorrestein, Pieter C.

    2013-01-01

    The communities constituting our microbiotas are emerging as mediators of the health-disease continuum. However, deciphering the functional impact of microbial communities on host pathophysiology represents a formidable challenge, due to the heterogeneous distribution of chemical and microbial species within the gastrointestinal (GI) tract. Herein, we apply imaging mass spectrometry (IMS) to localize metabolites from the interaction between the host and colonizing microbiota. This approach complements other molecular imaging methodologies in that analytes need not be known a priori, offering the possibility of untargeted analysis. Localized molecules within the GI tract were then identified in situ by surface sampling with nano-desorption electrospray ionization (nanoDESI) FT-MS. Products from diverse structural classes were identified including cholesterol-derived lipids, glycans, and polar metabolites. Specific chemical transformations performed by the microbiota were validated with bacteria in culture. This study illustrates how untargeted spatial characterization of metabolites can be applied to the molecular dissection of complex biology in situ. PMID:23009651

  18. Direct identification of various copper phthalocyanine pigments in automotive paints and paint smears by laser desorption ionization mass spectrometry.

    PubMed

    Mukai, Tadashi; Nakazumi, Hiroyuki; Kawabata, Shin-ichirou; Kusatani, Masaru; Nakai, Seita; Honda, Sadao

    2008-01-01

    Direct identification of copper phthalocyanine (CuPc) and chlorinated CuPcs in paints for discrimination between blue automobile paints by means of laser desorption mass spectrometry (LDMS) in the absence of a matrix is reported. The models consisted of eight commercially available CuPc pigments applied to a piece of plain white coating paper. The relationship between the peak intensity at m/z 575 of the CuPc, the number of pulsed laser shots, and laser power was compared to optimize laser abrasion. LDMS analysis of the model paints demonstrated that all characteristic components of the CuPc pigments in the paint films were in good agreement with those in the powder pigments. Further, the chlorinated CuPcs in the paint films could be distinguished. A quantity of 42 blue paint films, representing the paints used for painting Japanese domestic trucks, was examined by LDMS analysis. Results indicate that the paints can be classified into four categories based on the chlorinated CuPc components of the paints. Therefore, LDMS spectra of CuPc pigments would be useful for the identification of paints in forensic investigations. Herein, we report the successful identification of the CuPcs in a paint smear on the frame of a bicycle damaged in a hit-and-run accident, using the LDMS spectra.

  19. Towards the integration of matrix assisted laser desorption ionisation mass spectrometry imaging into the current fingermark examination workflow.

    PubMed

    Bradshaw, Robert; Bleay, Stephen; Wolstenholme, Rosalind; Clench, Malcolm Ronald; Francese, Simona

    2013-10-10

    A wide range of fingermark enhancement techniques (FET) is currently employed to visualise latent fingermarks at crime scenes. However, if smudged, partial, distorted or absent in the National Fingerprint Database, crime scene marks may be not useful for identification purposes. In these circumstances, a technology enabling chemical imaging of both endogenous and exogenous species contained within the fingermark could provide additional and associative investigative information, to profile the suspect's activities prior to the crime. Matrix Assisted Laser Desorption Ionisation Mass Spectrometry Imaging (MALDI MSI) has proven to be such a technique, enabling investigative information to be gathered, for example, on what substances the donor has come in contact with and what they have ingested. Nonetheless, to be employed, MALDI MSI has to be validated and its compatibility with FET tested for integration into the standard fingermark examination workflow. For the first time, a direct comparison has been made between the efficiency of a range of FET and MALDI MSI under different conditions. This information will build towards validation of the technology. Also, for the first time, MALDI MSI has been successfully employed as a sequential step following fingermark enhancement using many of the currently employed FET. Additionally, known enhancers have been "re-visited" by combining them with a MALDI matrix, providing both improved fingermark development and chemical species detection via MALDI MSI. The result reported here are good indication in favour of the integration of MALDI MSI into the current fingermark examination workflow for gathering additional investigative information.

  20. Direct detection of illicit drugs from biological fluids by desorption/ionization mass spectrometry with nanoporous silicon microparticles.

    PubMed

    Guinan, T M; Kirkbride, P; Della Vedova, C B; Kershaw, S G; Kobus, H; Voelcker, N H

    2015-12-01

    Surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) is a high throughput analytical technique capable of detecting low molecular weight analytes, including illicit drugs, and with potential applications in forensic toxicology as well as athlete and workplace testing, particularly for biological fluids (oral fluids, urine and blood). However, successful detection of illicit drugs using SALDI-MS often requires extraction steps to reduce the inherent complexity of biological fluids. Here, we demonstrate an all-in-one extraction and analytical system consisting of hydrophobically functionalized porous silicon microparticles (pSi-MPs) for affinity SALDI-MS of prescription and illicit drugs. This novel approach allows for the analysis of drugs from multiple biological fluids without sample preparation protocols. The effect of pSi-MP size, pore diameter, pore depth and functionalization on analytical performance is investigated. pSi-MPs were optimized for the rapid and high sensitivity detection of methadone, cocaine and 3,4-methylenedioxymethamphetamine (MDMA). This optimized system allowed extraction and detection of methadone from spiked saliva and clinical urine samples. Furthermore, by detecting oxycodone in additional clinical saliva and plasma samples, we were able to demonstrate the versatility of the pSi-MP SALDI-MS technique. PMID:26502296

  1. Glycine Identification in Natural Jarosites Using Laser Desorption Fourier Transform Mass Spectrometry: Implications for the Search for Life on Mars

    NASA Astrophysics Data System (ADS)

    Kotler, J. Michelle; Hinman, Nancy W.; Yan, Beizhan; Stoner, Daphne L.; Scott, Jill R.

    2008-04-01

    The jarosite group minerals have received increasing attention since the discovery of jarosite on the martian surface by the Mars Exploration Rover Opportunity. Given that jarosite can incorporate foreign ions within its structure, we have investigated the use of jarosite as an indicator of aqueous and biological processes on Earth and Mars. The use of laser desorption Fourier transform mass spectrometry has revealed the presence of organic matter in several jarosite samples from various locations worldwide. One of the ions from the natural jarosites has been attributed to glycine because it was systematically observed in combinations of glycine with synthetic ammonium and potassium jarosites, Na2SO4 and K2SO4. The ability to observe these organic signatures in jarosite samples with an in situ instrumental technique, such as the one employed in this study, furthers the goals of planetary geologists to determine whether signs of life (e.g., the presence of biomolecules or biomolecule precursors) can be detected in the rock record of terrestrial and extraterrestrial samples.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Identification of a variety of Staphylococcus species by matrix-assisted laser desorption ionization-time of flight mass spectrometry.

    PubMed

    Dubois, Damien; Leyssene, David; Chacornac, Jean Paul; Kostrzewa, Markus; Schmit, Pierre Olivier; Talon, Régine; Bonnet, Richard; Delmas, Julien

    2010-03-01

    Whole-cell fingerprinting by matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) in combination with a dedicated bioinformatic software tool (MALDI Biotyper 2.0) was used to identify 152 staphylococcal strains corresponding to 22 staphylococcal species. Spectra of the 152 isolates, previously identified at the species level using a sodA gene-based oligonucleotide array, were analyzed against the main spectra of 3,030 microorganisms. A total of 151 strains out of 152 (99.3%) were correctly identified at the species level; only one strain was identified at the genus level. The MALDI-TOF MS method revealed different clonal lineages of Staphylococcus epidermidis that were of either human or environmental origin, which suggests that the MALDI-TOF MS method could be useful in the profiling of staphylococcal strains. The topology of the dendrogram generated by the MALDI Biotyper 2.0 software from the spectra of 120 Staphylococcus reference strains (representing 36 species) was in general agreement with that inferred from the 16S rRNA gene-based analysis. Our findings indicate that the MALDI-TOF MS technology, associated with a broad-spectrum reference database, is an effective tool for the swift and reliable identification of Staphylococci.

  4. Optimization of Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry Analysis for Bacterial Identification

    PubMed Central

    Khot, Prasanna D.; Couturier, Marc R.; Wilson, Andrew; Croft, Ann

    2012-01-01

    Matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) is a relatively new addition to the clinical microbiology laboratory. The performance of the MALDI Biotyper system (Bruker Daltonics) was compared to those of phenotypic and genotypic identification methods for 690 routine and referred clinical isolates representing 102 genera and 225 unique species. We systematically compared direct-smear and extraction methods on a taxonomically diverse collection of isolates. The optimal score thresholds for bacterial identification were determined, and an approach to address multiple divergent results above these thresholds was evaluated. Analysis of identification scores revealed optimal species- and genus-level identification thresholds of 1.9 and 1.7, with 91.9% and 97.0% of isolates correctly identified to species and genus levels, respectively. Not surprisingly, routinely encountered isolates showed higher concordance than did uncommon isolates. The extraction method yielded higher scores than the direct-smear method for 78.3% of isolates. Incorrect species were reported in the top 10 results for 19.4% of isolates, and although there was no obvious cutoff to eliminate all of these ambiguities, a 10% score differential between the top match and additional species may be useful to limit the need for additional testing to reach single-species-level identifications. PMID:22993178

  5. Differentiation of Aeromonas isolated from drinking water distribution systems using matrix-assisted laser desorption/ionization-mass spectrometry.

    PubMed

    Donohue, Maura J; Best, Jennifer M; Smallwood, Anthony W; Kostich, Mitchell; Rodgers, Mark; Shoemaker, Jody A

    2007-03-01

    The genus Aeromonas is one of several medically significant genera that have gained prominence due to their evolving taxonomy and controversial role in human diseases. In this study, matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) was used to analyze the whole cells of both reference strains and unknown Aeromonas isolates obtained from water distribution systems. A library of over 45 unique m/z signatures was created from 40 strains that are representative of the 17 recognized species of Aeromonas, as well as 3 reference strains from genus Vibrio and 2 reference strains from Plesiomonas shigelloides. The library was used to help speciate 52 isolates of Aeromonas. The environmental isolates were broken up into 2 blind studies. Group 1 contained isolates that had a recognizable phenotypic profile and group 2 contained isolates that had an atypical phenotypic profile. MALDI-MS analysis of the water isolates in group 1 matched the phenotypic identification in all cases. In group 2, the MALDI-MS-based determination confirmed the identity of 18 of the 27 isolates. These results demonstrate that MALDI-MS analysis can rapidly and accurately classify species of the genus Aeromonas, making it a powerful tool especially suited for environmental monitoring and detection of microbial hazards in drinking water.

  6. Direct matrix-assisted laser desorption ionization time-of-flight mass spectrometry improves appropriateness of antibiotic treatment of bacteremia.

    PubMed

    Vlek, Anne L M; Bonten, Marc J M; Boel, C H Edwin

    2012-01-01

    Matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) allows the identification of microorganisms directly from positive blood culture broths. Use of the MALDI-TOF MS for rapid identification of microorganisms from blood culture broths can reduce the turnaround time to identification and may lead to earlier appropriate treatment of bacteremia. During February and April 2010, direct MALDI-TOF MS was routinely performed on all positive blood cultures. During December 2009 and March 2010 no direct MALDI-TOF MS was used. Information on antibiotic therapy was collected from the hospital and intensive care units' information systems from all positive blood cultures during the study period. In total, 253 episodes of bacteremia were included of which 89 during the intervention period and 164 during the control period. Direct performance of MALDI-TOF MS on positive blood culture broths reduced the time till species identification by 28.8-h and was associated with an 11.3% increase in the proportion of patients receiving appropriate antibiotic treatment 24 hours after blood culture positivity (64.0% in the control period versus 75.3% in the intervention period (p0.01)). Routine implementation of this technique increased the proportion of patients on adequate antimicrobial treatment within 24 hours.

  7. Direct detection of illicit drugs from biological fluids by desorption/ionization mass spectrometry with nanoporous silicon microparticles.

    PubMed

    Guinan, T M; Kirkbride, P; Della Vedova, C B; Kershaw, S G; Kobus, H; Voelcker, N H

    2015-12-01

    Surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) is a high throughput analytical technique capable of detecting low molecular weight analytes, including illicit drugs, and with potential applications in forensic toxicology as well as athlete and workplace testing, particularly for biological fluids (oral fluids, urine and blood). However, successful detection of illicit drugs using SALDI-MS often requires extraction steps to reduce the inherent complexity of biological fluids. Here, we demonstrate an all-in-one extraction and analytical system consisting of hydrophobically functionalized porous silicon microparticles (pSi-MPs) for affinity SALDI-MS of prescription and illicit drugs. This novel approach allows for the analysis of drugs from multiple biological fluids without sample preparation protocols. The effect of pSi-MP size, pore diameter, pore depth and functionalization on analytical performance is investigated. pSi-MPs were optimized for the rapid and high sensitivity detection of methadone, cocaine and 3,4-methylenedioxymethamphetamine (MDMA). This optimized system allowed extraction and detection of methadone from spiked saliva and clinical urine samples. Furthermore, by detecting oxycodone in additional clinical saliva and plasma samples, we were able to demonstrate the versatility of the pSi-MP SALDI-MS technique.

  8. High throughput screening of genetic polymorphisms by matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

    PubMed

    Corona, Giuseppe; Toffoli, Giuseppe

    2004-12-01

    In the post genomic era, the screening of many different genetic polymorphisms in large populations represents a major goal that will facilitate the understanding of individual genetic variability in the development of multi factor diseases and in drug response and toxicities. The increasing interest in these pathogenetic and pharmacogenomic studies by both academic and pharmaceutical industry researchers has increased the demand for broad genome association studies. This demand has produced a boom in the development of new and robust high throughput screening methods for genotype analysis. Matrix-assisted laser-desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) represents an emerging and powerful technique for DNA analysis because of its high speed, accuracy, no label requirement, and cost-effectiveness. So far, many MALDI-TOF MS approaches have been developed for rapid screening of single nucleotide polymorphisms (SNPs), variable sequences repeat, epigenotype analysis, quantitative allele studies, and for the discovery of new genetic polymorphisms. The more established methods are based on single base primer extension and minisequencing implemented with new chemical features to overcome the limitations associated with DNA analysis using MALDI-TOF MS. These new promising methods of genotyping include both photochemical and other different chemical and enzyme cleavage strategies that facilitate sample automation and MS analysis for both real-time genotyping and resequencing screening. In this review, we analyze and discuss in depth the advantages and the limitations of the more recent developments in MALDI-TOF MS analysis for large-scale genomic studies applications.

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

    PubMed

    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. Graphical Abstract ᅟ. PMID:27380389

  10. Quantitative mass spectrometry imaging of small-molecule neurotransmitters in rat brain tissue sections using nanospray desorption electrospray ionization.

    PubMed

    Bergman, Hilde-Marléne; Lundin, Erik; Andersson, Malin; Lanekoff, Ingela

    2016-06-01

    Small molecule neurotransmitters are essential for the function of the nervous system, and neurotransmitter imbalances are often connected to neurological disorders. The ability to quantify such imbalances is important to provide insights into the biochemical mechanisms underlying the disorder. This proof-of-principle study presents online quantification of small molecule neurotransmitters, specifically acetylcholine, γ-aminobutyric acid (GABA) and glutamate, in rat brain tissue sections using nanospray desorption electrospray ionization (nano-DESI) mass spectrometry imaging. By incorporating deuterated internal standards in the nano-DESI solvent we show identification, accurate mapping, and quantification of these small neurotransmitters in rat brain tissue without introducing any additional sample preparation steps. We find that GABA is about twice as abundant in the medial septum-diagonal band complex (MSDB) as in the cortex, while glutamate is about twice as abundant in the cortex as compared to the MSDB. The study shows that nano-DESI is well suited for imaging of small molecule neurotransmitters in health and disease. PMID:26859000

  11. Rapid differentiation of Panax ginseng and Panax quinquefolius by matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Lai, Ying-Han; So, Pui-Kin; Lo, Samual Chun-Lap; Ng, Eddy Wing Yin; Poon, Terence Chuen Wai; Yao, Zhong-Ping

    2012-11-13

    A matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS)-based method has been developed for rapid differentiation between Panax ginseng and Panax quinquefolius, two herbal medicines with similar chemical and physical properties but different therapeutic effects. This method required only a small quantity of samples, and the herbal medicines were analyzed by MALDI-MS either after a brief extraction step, or directly on the powder form or small pieces of raw samples. The acquired MALDI-MS spectra showed different patterns of ginsenosides and small chemical molecules between P. ginseng and P. quinquefolius, thus allowing unambiguous differentiation between the two Panax species based on the specific ions, intensity ratios of characteristic ions or principal component analysis. The approach could also be used to differentiate red ginseng or P. quinquefolius adulterated with P. ginseng from pure P. ginseng and pure Panax quinquefolium. The intensity ratios of characteristic ions in the MALDI-MS spectra showed high reproducibility and enabled quantitative determination of ginsenosides in the herbal samples and percentage of P. quinquefolius in the adulterated binary mixture. The method is simple, rapid, robust, and can be extended for analysis of other herbal medicines.

  12. TOPICAL REVIEW: Breathing mode excitation in near-harmonic systems: resonant mass capture, desorption and atoms in optical lattices

    NASA Astrophysics Data System (ADS)

    Gadzuk, J. W.

    1998-09-01

    The phenomenon of breathing mode excitation or bound-state wavepacket squeezing and spreading driven by a time-dependent oscillator frequency (due to either a transient force constant or mass) is considered here. An easily implemented theory of stimulated wavepacket dynamics for near-harmonic systems is presented which describes a variety of generic time dependences such as single sudden excitation, double switching (excitation/time delay/de-excitation) and decaying initially excited states which characterize many processes in spectroscopy, pump-probe control in intramolecular dynamics, and femtochemistry. The model is used as the theoretical basis for understanding such diverse phenomena as quantum excitation due to temporary neutron capture, stimulated bond-breaking resulting in delocalization, desorption, or dissociation, and breathing mode excitation of ultracold atoms trapped in optical lattices. Whilst the first two examples are speculative, results for transient wavepacket dynamics of the occupied excited optical lattice are in accord with recent experimental observations reported by the NIST Laser Cooling Group. Emphasis on the inherent theoretical simplicity and the multidisciplinary aspects of near-harmonic breathing mode excitation, as exemplified by the specific realizations considered here, has been a major intent of this topical review.

  13. Rapid screening of mixed edible oils and gutter oils by matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Ng, Tsz-Tsun; So, Pui-Kin; Zheng, Bo; Yao, Zhong-Ping

    2015-07-16

    Authentication of edible oils is a long-term issue in food safety, and becomes particularly important with the emergence and wide spread of gutter oils in recent years. Due to the very high analytical demand and diversity of gutter oils, a high throughput analytical method and a versatile strategy for authentication of mixed edible oils and gutter oils are highly desirable. In this study, an improved matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) method has been developed for direct analysis of edible oils. This method involved on-target sample loading, automatic data acquisition and simple data processing. MALDI-MS spectra with high quality and high reproducibility have been obtained using this method, and a preliminary spectral database of edible oils has been set up. The authenticity of an edible oil sample can be determined by comparing its MALDI-MS spectrum and principal component analysis (PCA) results with those of its labeled oil in the database. This method is simple and the whole process only takes several minutes for analysis of one oil sample. We demonstrated that the method was sensitive to change in oil compositions and can be used for measuring compositions of mixed oils. The capability of the method for determining mislabeling enables it for rapid screening of gutter oils since fraudulent mislabeling is a common feature of gutter oils. PMID:26073811

  14. Screening of the binding of small molecules to proteins by desorption electrospray ionization mass spectrometry combined with protein microarray.

    PubMed

    Yao, Chenxi; Wang, Tao; Zhang, Buqing; He, Dacheng; Na, Na; Ouyang, Jin

    2015-11-01

    The interaction between bioactive small molecule ligands and proteins is one of the important research areas in proteomics. Herein, a simple and rapid method is established to screen small ligands that bind to proteins. We designed an agarose slide to immobilize different proteins. The protein microarrays were allowed to interact with different small ligands, and after washing, the microarrays were screened by desorption electrospray ionization mass spectrometry (DESI MS). This method can be applied to screen specific protein binding ligands and was shown for seven proteins and 34 known ligands for these proteins. In addition, a high-throughput screening was achieved, with the analysis requiring approximately 4 s for one sample spot. We then applied this method to determine the binding between the important protein matrix metalloproteinase-9 (MMP-9) and 88 small compounds. The molecular docking results confirmed the MS results, demonstrating that this method is suitable for the rapid and accurate screening of ligands binding to proteins. Graphical Abstract ᅟ. PMID:26174365

  15. Development of analysis of volatile polyfluorinated alkyl substances in indoor air using thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Wu, Yaoxing; Chang, Victor W-C

    2012-05-18

    The study attempts to utilize thermal desorption (TD) coupled with gas chromatography-mass spectrometry (GC-MS) for determination of indoor airborne volatile polyfluorinated alkyl substances (PFASs), including four fluorinated alcohols (FTOHs), two fluorooctane sulfonamides (FOSAs), and two fluorooctane sulfonamidoethanols (FOSEs). Standard stainless steel tubes of Tenax/Carbograph 1 TD were employed for low-volume sampling and exhibited minimal breakthrough of target analytes in sample collection. The method recoveries were in the range of 88-119% for FTOHs, 86-138% for FOSAs, exhibiting significant improvement compared with other existing air sampling methods. However, the widely reported high method recoveries of FOSEs were also observed (139-210%), which was probably due to the structural differences between FOSEs and internal standards. Method detection limit, repeatability, linearity, and accuracy were reported as well. The approach has been successfully applied to routine quantification of targeted PFASs in indoor environment of Singapore. The significantly shorter sampling time enabled the observation of variations of concentrations of targeted PFASs within different periods of a day, with higher concentration levels at night while ventilation systems were shut off. This indicated the existence of indoor sources and the importance of building ventilation and air conditioning system.

  16. Lipid imaging within the normal rat kidney using silver nanoparticles by matrix-assisted laser desorption/ionization mass spectrometry

    PubMed Central

    Muller, Ludovic; Kailas, Ajay; Jackson, Shelley N.; Roux, Aurelie; Barbacci, Damon; Schultz, J. Albert; Balaban, Carey; Woods, Amina S.

    2015-01-01

    The well-characterized cellular and structural components of the kidney show distinct regional compositions and distribution of lipids. In order to more fully analyze the renal lipidome we developed a matrix-assisted laser desorption/ionization mass spectrometry approach for imaging that may be used to pinpoint sites of changes from normal in pathological conditions. This was accomplished by implanting sagittal cryostat rat kidney sections with a stable, quantifiable and reproducible uniform layer of silver using a magnetron sputtering source to form silver nanoparticles. Thirty-eight lipid species including 7 ceramides, 8 diacylglycerols, 22 triacylglycerols, and cholesterol were detected and imaged in positive ion mode. Thirty-six lipid species consisting of, 7 sphingomyelins, 10 phosphatidylethanolamines, 1 phosphatidylglycerol, 7 phosphatidylinositols and 11 sulfatides, were imaged in negative ion mode for a total of seventy-four high resolution lipidome maps of the normal kidney. Thus, our approach is a powerful tool not only for studying structural changes in animal models of disease, but also for diagnosing and tracking stages of disease in human kidney tissue biopsies. PMID:25671768

  17. Mass spectrometry detection and imaging of inorganic and organic explosive device signatures using desorption electro-flow focusing ionization.

    PubMed

    Forbes, Thomas P; Sisco, Edward

    2014-08-01

    We demonstrate the coupling of desorption electro-flow focusing ionization (DEFFI) with in-source collision induced dissociation (CID) for the mass spectrometric (MS) detection and imaging of explosive device components, including both inorganic and organic explosives and energetic materials. We utilize in-source CID to enhance ion collisions with atmospheric gas, thereby reducing adducts and minimizing organic contaminants. Optimization of the MS signal response as a function of in-source CID potential demonstrated contrasting trends for the detection of inorganic and organic explosive device components. DEFFI-MS and in-source CID enabled isotopic and molecular speciation of inorganic components, providing further physicochemical information. The developed system facilitated the direct detection and chemical mapping of trace analytes collected with Nomex swabs and spatially resolved distributions within artificial fingerprints from forensic lift tape. The results presented here provide the forensic and security sectors a powerful tool for the detection, chemical imaging, and inorganic speciation of explosives device signatures. PMID:24968206

  18. Effects of Tailored Surface Chemistry on Desorption Electrospray Ionization Mass Spectrometry: a Surface-Analytical Study by XPS and AFM

    NASA Astrophysics Data System (ADS)

    Penna, Andrea; Careri, Maria; Spencer, Nicholas D.; Rossi, Antonella

    2015-08-01

    Since it was proposed for the first time, desorption electrospray ionization-mass spectrometry (DESI-MS) has been evaluated for applicability in numerous areas. Elucidations of the ionization mechanisms and the subsequent formation of isolated gas-phase ions have been proposed so far. In this context, the role of both surface and pneumatic effects on ion-formation yield has recently been investigated. Nevertheless, the effect of the surface chemistry has not yet been completely understood. Functionalized glass surfaces have been prepared, in order to tailor surface performance for ion formation. Three substrates were functionalized by depositing three different silanes [3-mercaptopropyltriethoxysilane (MTES), octyltriethoxysilane (OTES), and 1H,1H,2H,2H-perfluorooctyltriethoxy-silane (FOTES)] from toluene solution onto standard glass slides. Surface characterization was carried out by contact-angle measurements, tapping-mode atomic force microscopy, and X-ray photoelectron spectroscopy. Morphologically homogeneous and thickness-controlled films in the nm range were obtained, with surface free energies lying between 15 and 70 mJ/m2. These results are discussed, together with those of DESI-MS on low-molecular-weight compounds such as melamine, tetracycline, and lincomycin, also taking into account the effects of the sprayer potential and its correlation with surface wettability. The results demonstrate that ion-formation efficiency is affected by surface wettability, and this was demonstrated operating above and below the onset of the electrospray.

  19. Identification of phlebotomine sand flies (Diptera: Psychodidae) by matrix-assisted laser desorption/ionization time of flight mass spectrometry

    PubMed Central

    2014-01-01

    Background Phlebotomine sand flies are incriminated in the transmission of several human and veterinary pathogens. To elucidate their role as vectors, proper species identification is crucial. Since traditional morphological determination is based on minute and often dubious characteristics on their head and genitalia, which require certain expertise and may be damaged in the field-collected material, there is a demand for rapid, simple and cost-effective molecular approaches. Methods Six laboratory-reared colonies of phlebotomine sand flies belonging to five species and four subgenera (Phlebotomus, Paraphlebotomus, Larroussius, Adlerius) were used to evaluate the discriminatory power of matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS). Various storage conditions and treatments, including the homogenization in either distilled water or given concentrations of formic acid, were tested on samples of both sexes. Results Specimens of all five analysed sand fly species produced informative, reproducible and species-specific protein spectra that enabled their conclusive species identification. The method also distinguished between two P. sergenti colonies originating from different geographical localities. Protein profiles within a species were similar for specimens of both sexes. Tested conditions of specimen storage and sample preparation give ground to a standard protocol that is generally applicable on analyzed sand fly specimens. Conclusions Species identification of sand flies by MALDI-TOF MS is feasible and represents a novel promising tool to improve biological and epidemiological studies on these medically important insects. PMID:24423215

  20. Optimisation of the quantitative determination of chlormequat by matrix-assisted laser desorption/ionisation mass spectrometry.

    PubMed

    Horak, J; Werther, W; Schmid, E R

    2001-01-01

    The plant growth regulator chlormequat, an involatile quaternary ammonium salt, has been quantified by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS). Restrictions for quantitative MALDI-TOFMS analysis, such as irreproducible crystallisation and unsatisfactory laser stability, have been overcome by the application of two synthesised isotopically labelled standards and the optimisation of the measurement protocol. Data acquisition at constant laser power was compared to data acquisition at approximately constant ion abundance of the relevant ions (analyte and internal standards). Data acquisition at constant ion abundance performed better and enabled a high number of consecutive firings to the same sample deposition area. Furthermore an increased sample-to-sample repeatability and a high reproducibility over several weeks without re-calibration have been attained by this method. Linearity over three orders of magnitude (0.05 to 30 ng/microL chlormequat), with a correlation coefficient of 0.9997, was achieved using [13C3]-chlormequat as internal standard. Limit of detection and limit of determination were determined to be in the low pg/microL range for pure standard solutions. Thin-layer chromatography was applied for the removal of high amounts of choline, which is often present in plant tissue extracts and can adversely affect the ionisation and detection of chlormequat by MALDI-TOFMS. The use of two internal standards ([13C3]- and [2H9]-chlormequat) enabled direct quantification and simultaneous control of the recovery. PMID:11223954

  1. Direct Analysis of Triacylglycerols from Crude Lipid Mixtures by Gold Nanoparticle-Assisted Laser Desorption/Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Son, Jeongjin; Lee, Gwangbin; Cha, Sangwon

    2014-05-01

    Triacylglycerols (TAGs), essential energy storage lipids, are easily detected by conventional MALDI MS when occurring on their own. However, their signals are easily overwhelmed by other lipids, mainly phosphatidylcholines (PCs) and, therefore, require purification. In order to profile TAGs from crude lipid mixtures without prefractionation, we investigated alternative matrixes that can suppress phospholipid ion signals and enhance cationization of TAGs. We found that an aqueous solution of citrate-capped gold nanoparticles (AuNPs) with a diameter of 12 nm is a superior matrix for the laser desorption/ionization mass spectrometry (LDI MS) of TAGs in crude lipid mixtures. The AuNP matrix effectively suppressed other lipid signals such as phospholipids and also provided 100 times lower detection limit for TAGs than 2,5-dihydroxybenzoic acid (DHB), the best conventional MALDI matrix for TAGs. The AuNP-assisted LDI MS enabled us to obtain detailed TAG profiles including minor species directly from crude beef lipid extracts without phospholipid interference. In addition, we could detect TAGs at a trace level from a total brain lipid extract.

  2. Improved Cell Typing by Charge-State Deconvolution of matrix-assisted laser desorption/ionization Mass Spectra

    SciTech Connect

    Wilkes, Jon G.; Buzantu, Dan A.; Dare, Diane J.; Dragan, Yvonne P.; Chiarelli, M. Paul; Holland, Ricky D.; Beaudoin, Michael; Heinze, Thomas M.; Nayak, Rajesh; Shvartsburg, Alexandre A.

    2006-05-30

    Robust, specific, and rapid identification of toxic strains of bacteria and viruses, to guide the mitigation of their adverse health effects and optimum implementation of other response actions, remains a major analytical challenge. This need has driven the development of methods for classification of microorganisms using mass spectrometry, particularly matrix-assisted laser desorption ionization MS (MALDI) that allows high throughput analyses with minimum sample preparation. We describe a novel approach to cell typing based on pattern recognition of MALDI spectra, which involves charge-state deconvolution in conjunction with a new correlation analysis procedure. The method is applicable to both prokaryotic and eukaryotic cells. Charge-state deconvolution improves the quantitative reproducibility of spectra because multiply-charged ions resulting from the same biomarker attaching a different number of protons are recognized and their abundances are combined. This allows a clearer distinction of bacterial strains or of cancerous and normal liver cells. Improved class distinction provided by charge-state deconvolution was demonstrated by cluster spacing on canonical variate score charts and by correlation analyses. Deconvolution may enhance detection of early disease state or therapy progress markers in various tissues analyzed by MALDI.

  3. Screening of the binding of small molecules to proteins by desorption electrospray ionization mass spectrometry combined with protein microarray.

    PubMed

    Yao, Chenxi; Wang, Tao; Zhang, Buqing; He, Dacheng; Na, Na; Ouyang, Jin

    2015-11-01

    The interaction between bioactive small molecule ligands and proteins is one of the important research areas in proteomics. Herein, a simple and rapid method is established to screen small ligands that bind to proteins. We designed an agarose slide to immobilize different proteins. The protein microarrays were allowed to interact with different small ligands, and after washing, the microarrays were screened by desorption electrospray ionization mass spectrometry (DESI MS). This method can be applied to screen specific protein binding ligands and was shown for seven proteins and 34 known ligands for these proteins. In addition, a high-throughput screening was achieved, with the analysis requiring approximately 4 s for one sample spot. We then applied this method to determine the binding between the important protein matrix metalloproteinase-9 (MMP-9) and 88 small compounds. The molecular docking results confirmed the MS results, demonstrating that this method is suitable for the rapid and accurate screening of ligands binding to proteins. Graphical Abstract ᅟ.

  4. Matrix-assisted laser desorption/ionization mass spectrometric analysis of aliphatic biodegradable photoluminescent polymers using new ionic liquid matrices.

    PubMed

    Serrano, Carlos A; Zhang, Yi; Yang, Jian; Schug, Kevin A

    2011-05-15

    In this study, two novel ionic liquid matrices (ILMs), N,N-diisopropylethylammonium 3-oxocoumarate and N,N-diisopropylethylammonium dihydroxymonooxoacetophenoate, were tested for the structural elucidation of recently developed aliphatic biodegradable polymers by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The polymers, formed by a condensation reaction of three components, citric acid, octane diol, and an amino acid, are fluorescent, but the exact mechanism behind their luminescent properties has not been fully elucidated. In the original studies, which introduced the polymer class (J. Yang et al., Proc. Natl. Acad. Sci. USA 2009, 106, 10086-10091), a hyper-conjugated cyclic structure was proposed as the source for the photoluminescent behavior. With the use of the two new ILMs, we present evidence that supports the presence of the proposed cyclization product. In addition, the new ILMs, when compared with a previously established ILM, N,N-diisopropylethylammonium α-cyano-3-hydroxycinnimate, provided similar signal intensities and maintained similar spectral profiles. This research also established that the new ILMs provided good spot-to-spot reproducibility and high ionization efficiency compared with corresponding crystalline matrix preparations. Many polymer features revealed through the use of the ILMs could not be observed with crystalline matrices. Ultimately, the new ILMs highlighted the composition of the synthetic polymers, as well as the loss of water that was expected for the formation of the proposed cyclic structure on the polymer backbone.

  5. 2-Hydrazinoquinoline: a reactive matrix for matrix-assisted laser desorption/ionization mass spectrometry to detect gaseous carbonyl compounds.

    PubMed

    Shigeri, Yasushi; Kamimura, Takuya; Ando, Masanori; Uegaki, Koichi; Sato, Hiroaki; Tani, Fumito; Arakawa, Ryuichi; Kinumi, Tomoya

    2016-01-01

    The sensitivity, range of applications, and reaction mechanism of 2-hydrazinoquinoline as a reactive matrix for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) were examined. Using a reaction chamber (125L) equipped with a stirring fan and a window for moving the MALDI-MS plate and volatile samples in and out, the sensitivities of 2-hydrazinoquinoline to gaseous aldehydes (formaldehyde, acetaldehyde, propionaldehyde, and n-butyraldehyde) and ketones (acetone, methyl ethyl ketone, and methyl isobutyl ketone) were determined to be at least parts per million (ppm) levels. On the other hand, carboxylic acids (formic acid, acetic acid, propionic acid, and butyric acid) and esters (ethyl acetate, pentyl acetate, isoamyl acetate, and methyl salicylate) could not be detected by 2-hydrazinoquinoline in MALDI-MS. In addition to 2,4-dinitrophenylhydrazine, a common derivatization reagent for analyzing carbonyl compounds quantitatively in gas chromatography and liquid chromatography, the dissolution of 2-hydrazinoquinoline in an acidic solution, such as trifluoroacetic acid, was essential for its function as a reactive matrix for MALDI- MS. PMID:27419901

  6. Sequence analysis of phosphorothioate oligonucleotides via matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

    PubMed

    Schuette, J M; Pieles, U; Maleknia, S D; Srivatsa, G S; Cole, D L; Moser, H E; Afeyan, N B

    1995-09-01

    Modification of the natural phosphodiester backbone of deoxyribooligonucleotides can impart increased biostability via nuclease resistance. Further, uniform incorporation of phosphorothioate linkages renders oligonucleotides highly resistant to reagents traditionally used in sequencing reactions. As a consequence, analytical tests crucial for establishing the identity of such oligonucleotide drugs are less informative. To circumvent this problem, chemical oxidation has been employed for converting the phosphorothioate to the uniform phosphodiester, thereby facilitating enzymatic degradation. Following oxidation, exonucleases which sequentially cleave individual bases from the 3' or 5' terminus of the oligonucleotide or base-specific cleavage chemicals were used to facilitate sequence identification of the oligonucleotide. Matrix-assisted laser desorption ionization-time-of-flight/mass spectrometry (MALDI-TOF/MS), previously used to sequence natural phosphodiester DNA, was then used to sequence the chemically oxidized phosphorothioate. Sequential enzymatic cleavage of desulphurized phosphorothioates in combination with MALDI analysis not only provides a viable alternative to radiolabeling as used in conventional sequencing approaches (e.g. Maxam-Gilbert), but also enables rapid sequencing of phosphorothioate oligonucleotides, for routine drug analysis. PMID:8562591

  7. Identification of Tsetse (Glossina spp.) Using Matrix-Assisted Laser Desorption/Ionisation Time of Flight Mass Spectrometry

    PubMed Central

    Hoppenheit, Antje; Murugaiyan, Jayaseelan; Bauer, Burkhard; Steuber, Stephan; Clausen, Peter-Henning; Roesler, Uwe

    2013-01-01

    Glossina (G.) spp. (Diptera: Glossinidae), known as tsetse flies, are vectors of African trypanosomes that cause sleeping sickness in humans and nagana in domestic livestock. Knowledge on tsetse distribution and accurate species identification help identify potential vector intervention sites. Morphological species identification of tsetse is challenging and sometimes not accurate. The matrix-assisted laser desorption/ionisation time of flight mass spectrometry (MALDI TOF MS) technique, already standardised for microbial identification, could become a standard method for tsetse fly diagnostics. Therefore, a unique spectra reference database was created for five lab-reared species of riverine-, savannah- and forest- type tsetse flies and incorporated with the commercial Biotyper 3.0 database. The standard formic acid/acetonitrile extraction of male and female whole insects and their body parts (head, thorax, abdomen, wings and legs) was used to obtain the flies' proteins. The computed composite correlation index and cluster analysis revealed the suitability of any tsetse body part for a rapid taxonomical identification. Phyloproteomic analysis revealed that the peak patterns of G. brevipalpis differed greatly from the other tsetse. This outcome was comparable to previous theories that they might be considered as a sister group to other tsetse spp. Freshly extracted samples were found to be matched at the species level. However, sex differentiation proved to be less reliable. Similarly processed samples of the common house fly Musca domestica (Diptera: Muscidae; strain: Lei) did not yield any match with the tsetse reference database. The inclusion of additional strains of morphologically defined wild caught flies of known origin and the availability of large-scale mass spectrometry data could facilitate rapid tsetse species identification in the future. PMID:23875040

  8. Rapid Identification of the Foodborne Pathogen Trichinella spp. by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry.

    PubMed

    Mayer-Scholl, Anne; Murugaiyan, Jayaseelan; Neumann, Jennifer; Bahn, Peter; Reckinger, Sabine; Nöckler, Karsten

    2016-01-01

    Human trichinellosis occurs through consumption of raw or inadequately processed meat or meat products containing larvae of the parasitic nematodes of the genus Trichinella. Currently, nine species and three genotypes are recognized, of which T. spiralis, T. britovi and T. pseudospiralis have the highest public health relevance. To date, the differentiation of the larvae to the species and genotype level is based primarily on molecular methods, which can be relatively time consuming and labor intensive. Due to its rapidness and ease of use a matrix assisted laser desorption / ionization time of flight mass spectrometry (MALDI-TOF MS) reference spectra database using Trichinella strains of all known species and genotypes was created. A formicacid/acetonitrile protein extraction was carried out after pooling 10 larvae of each Trichinella species and genotype. Each sample was spotted 9 times using α-cyano 4-hydoxy cinnamic acid matrix and a MicroFlex LT mass spectrometer was used to acquire 3 spectra (m/z 2000 to 20000 Da) from each spot resulting in 27 spectra/species or genotype. Following the spectra quality assessment, Biotyper software was used to create a main spectra library (MSP) representing nine species and three genotypes of Trichinella. The evaluation of the spectra generated by MALDI-TOF MS revealed a classification which was comparable to the results obtained by molecular methods. Also, each Trichinella species utilized in this study was distinct and distinguishable with a high confidence level. Further, different conservation methods such as freezing and conservation in alcohol and the host species origin of the isolated larvae did not have a significant influence on the generated spectra. Therefore, the described MALDI-TOF MS can successfully be implemented for both genus and species level identification and represents a major step forward in the use of this technique in foodborne parasitology.

  9. Identification of beer-spoilage bacteria using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Wieme, Anneleen D; Spitaels, Freek; Aerts, Maarten; De Bruyne, Katrien; Van Landschoot, Anita; Vandamme, Peter

    2014-08-18

    Applicability of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) for identification of beer-spoilage bacteria was examined. To achieve this, an extensive identification database was constructed comprising more than 4200 mass spectra, including biological and technical replicates derived from 273 acetic acid bacteria (AAB) and lactic acid bacteria (LAB), covering a total of 52 species, grown on at least three growth media. Sequence analysis of protein coding genes was used to verify aberrant MALDI-TOF MS identification results and confirmed the earlier misidentification of 34 AAB and LAB strains. In total, 348 isolates were collected from culture media inoculated with 14 spoiled beer and brewery samples. Peak-based numerical analysis of MALDI-TOF MS spectra allowed a straightforward species identification of 327 (94.0%) isolates. The remaining isolates clustered separately and were assigned through sequence analysis of protein coding genes either to species not known as beer-spoilage bacteria, and thus not present in the database, or to novel AAB species. An alternative, classifier-based approach for the identification of spoilage bacteria was evaluated by combining the identification results obtained through peak-based cluster analysis and sequence analysis of protein coding genes as a standard. In total, 263 out of 348 isolates (75.6%) were correctly identified at species level and 24 isolates (6.9%) were misidentified. In addition, the identification results of 50 isolates (14.4%) were considered unreliable, and 11 isolates (3.2%) could not be identified. The present study demonstrated that MALDI-TOF MS is well-suited for the rapid, high-throughput and accurate identification of bacteria isolated from spoiled beer and brewery samples, which makes the technique appropriate for routine microbial quality control in the brewing industry. PMID:24929682

  10. Identification of beer-spoilage bacteria using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Wieme, Anneleen D; Spitaels, Freek; Aerts, Maarten; De Bruyne, Katrien; Van Landschoot, Anita; Vandamme, Peter

    2014-08-18

    Applicability of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) for identification of beer-spoilage bacteria was examined. To achieve this, an extensive identification database was constructed comprising more than 4200 mass spectra, including biological and technical replicates derived from 273 acetic acid bacteria (AAB) and lactic acid bacteria (LAB), covering a total of 52 species, grown on at least three growth media. Sequence analysis of protein coding genes was used to verify aberrant MALDI-TOF MS identification results and confirmed the earlier misidentification of 34 AAB and LAB strains. In total, 348 isolates were collected from culture media inoculated with 14 spoiled beer and brewery samples. Peak-based numerical analysis of MALDI-TOF MS spectra allowed a straightforward species identification of 327 (94.0%) isolates. The remaining isolates clustered separately and were assigned through sequence analysis of protein coding genes either to species not known as beer-spoilage bacteria, and thus not present in the database, or to novel AAB species. An alternative, classifier-based approach for the identification of spoilage bacteria was evaluated by combining the identification results obtained through peak-based cluster analysis and sequence analysis of protein coding genes as a standard. In total, 263 out of 348 isolates (75.6%) were correctly identified at species level and 24 isolates (6.9%) were misidentified. In addition, the identification results of 50 isolates (14.4%) were considered unreliable, and 11 isolates (3.2%) could not be identified. The present study demonstrated that MALDI-TOF MS is well-suited for the rapid, high-throughput and accurate identification of bacteria isolated from spoiled beer and brewery samples, which makes the technique appropriate for routine microbial quality control in the brewing industry.

  11. Plasma desorption mass spectrometry in studies of formation and sputtering of fullerenes by MeV atomic ions

    NASA Astrophysics Data System (ADS)

    Bitensky, I.; Brinkmalm, G.; Demirev, P.; Eriksson, J.; H»Kansson, P.; Papaléo, R.; Sundqvist, B. U. R.; Zubarev, R.

    1994-10-01

    An account is presented on plasma desorption mass spectrometry (PDMS) studies of different carbon-containing organic solids utilizing megaelectronvolt (MeV) atomic ions from the Uppsvala EN-tandem accelerator. Positive ions of even-numbered carbon clusters (C+n, n = 40 to> 200) are ejected as a result of the interaction of the fast MeV ions with the target. The distribution of cluster sizes suggests that stable, closed carbon-cage structures -- fullerenes - are formed. Among the investigated materials that produce carbon clusters are poly(vinylidenefluoride) and fluorinated fullerenes -- C60F2m. For comparison purposes data from C60 targets have been also collected and analyzed. PDMS has been used for the in situ assessment of the damaging of C60 films by MeV heavy ions. Results on delayed electron emission from C-60 sputtered by MeV ions from C60 fullerene targets are also presented. A model of fullerene formation as a result of MeV ion interactions with the organic solid, including the yield dependence on primary ion charge state, is summarized. Both the data and the model suggest that fullerenes are formed as a result of a single primary ion impact and that they are ejected from an axially expanding infratrack plasma region. Results on different types of coalescence reactions in synthetic C60 fullerene targets and in blends of pure (synthetic) C60 with polystyrene leading to ejection of higher mass positive fullerene ions (C+k, k from 60 to more than 200) are also reported. The coalescence reactions are induced by the interaction of a single MeV ion with the solid. We argue that our data contribute to elucidating some general patterns of the fullerene formation mechanism.

  12. Removal of sodium dodecyl sulfate from protein samples prior to matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Puchades, M; Westman, A; Blennow, K; Davidsson, P

    1999-01-01

    Sodium dodecyl sulfate (SDS) is widely used for protein solubilization and for separation of proteins by SDS polyacrylamide gel electrophoresis (SDS-PAGE). However, SDS interferes with other techniques used for characterization of proteins, such as mass spectrometry (MS) and amino acid sequencing. In this paper, we have compared three procedures to remove SDS from proteins, including chloroform/methanol/water extraction (C/M/W), cold acetone extraction and desalting columns, in order to find a rapid and reproducible procedure that provides sufficient reduction of SDS and high recovery rates for proteins prior to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). A 1000-fold reduction of SDS concentration and a protein recovery at approximately 50% were obtained with the C/M/W procedure. The cold acetone procedure gave a 100-fold reduction of SDS and a protein recovery of approximately 80%. By using desalting columns, the removal of SDS was 100-fold, with a protein recovery of nearly 50%. Both the C/M/W and the cold acetone methods provided sufficient reduction of SDS, high recovery rates of protein and allowed the acquisition of MALDI spectra. The use of n-octyl-beta-D-glucopyranoside in the protein sample preparation enhanced the MALDI signal for protein samples containing more than 2 10(-4)% SDS, after the C/M/W extraction. Following the cold acetone procedure, the use of n-octylglucoside was found to be necessary in order to obtain spectra, but they were of lower quality than those obtained with the C/M/W method, probably due to higher residual amounts of SDS. PMID:10209872

  13. Total microcystins analysis in water using laser diode thermal desorption-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Roy-Lachapelle, Audrey; Fayad, Paul B; Sinotte, Marc; Deblois, Christian; Sauvé, Sébastien

    2014-04-11

    A new approach for the analysis of the cyanobacterial microcystins (MCs) in environmental water matrices has been developed. It offers a cost efficient alternative method for the fast quantification of total MCs using mass spectrometry. This approach permits the quantification of total MCs concentrations without requiring any derivatization or the use of a suite of MCs standards. The oxidation product 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) was formed through a Lemieux oxidation and represented the total concentration of free and bound MCs in water samples. MMPB was analyzed using laser diode thermal desorption-atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). LDTD is a robust and reliable sample introduction method with ultra-fast analysis time (<15 s sample(-1)). Several oxidation and LDTD parameters were optimized to improve recoveries and signal intensity. MCs oxidation recovery yield was 103%, showing a complete reaction. Internal calibration with standard addition was achieved with the use of 4-phenylbutyric acid (4-PB) as internal standard and showed good linearity (R(2)>0.999). Limits of detection and quantification were 0.2 and 0.9 μg L(-1), respectively. These values are comparable with the WHO (World Health Organization) guideline of 1 μg L(-1) for total microcystin-LR congener in drinking water. Accuracy and interday/intraday variation coefficients were below 15%. Matrix effect was determined with a recovery of 91%, showing no significant signal suppression. This work demonstrates the use of the LDTD-APCI-MS/MS interface for the screening, detection and quantification of total MCs in complex environmental matrices.

  14. Rapid Identification of the Foodborne Pathogen Trichinella spp. by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

    PubMed Central

    Mayer-Scholl, Anne; Murugaiyan, Jayaseelan; Neumann, Jennifer; Bahn, Peter; Reckinger, Sabine; Nöckler, Karsten

    2016-01-01

    Human trichinellosis occurs through consumption of raw or inadequately processed meat or meat products containing larvae of the parasitic nematodes of the genus Trichinella. Currently, nine species and three genotypes are recognized, of which T. spiralis, T. britovi and T. pseudospiralis have the highest public health relevance. To date, the differentiation of the larvae to the species and genotype level is based primarily on molecular methods, which can be relatively time consuming and labor intensive. Due to its rapidness and ease of use a matrix assisted laser desorption / ionization time of flight mass spectrometry (MALDI-TOF MS) reference spectra database using Trichinella strains of all known species and genotypes was created. A formicacid/acetonitrile protein extraction was carried out after pooling 10 larvae of each Trichinella species and genotype. Each sample was spotted 9 times using α-cyano 4-hydoxy cinnamic acid matrix and a MicroFlex LT mass spectrometer was used to acquire 3 spectra (m/z 2000 to 20000 Da) from each spot resulting in 27 spectra/species or genotype. Following the spectra quality assessment, Biotyper software was used to create a main spectra library (MSP) representing nine species and three genotypes of Trichinella. The evaluation of the spectra generated by MALDI-TOF MS revealed a classification which was comparable to the results obtained by molecular methods. Also, each Trichinella species utilized in this study was distinct and distinguishable with a high confidence level. Further, different conservation methods such as freezing and conservation in alcohol and the host species origin of the isolated larvae did not have a significant influence on the generated spectra. Therefore, the described MALDI-TOF MS can successfully be implemented for both genus and species level identification and represents a major step forward in the use of this technique in foodborne parasitology. PMID:26999436

  15. Characterization of pyrogenic black carbon by desorption atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Podgorski, David C; Hamdan, Rasha; McKenna, Amy M; Nyadong, Leonard; Rodgers, Ryan P; Marshall, Alan G; Cooper, William T

    2012-02-01

    We present a new method for molecular characterization of intact biochar directly, without sample preparation or pretreatment, on the basis of desorption atmospheric pressure photoionization (DAPPI) coupled to Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. Conventional ionization methods (e.g., electrospray or atmospheric pressure photoionization) for characterization of natural organic matter have limited utility for the characterization of chars due to incomplete solubility in common solvents. Therefore, direct ionization techniques that do not require sample dissolution prior to analysis are ideal. Here, we apply DAPPI FTICR mass spectrometry to enable the first molecular characterization of uncharred parent oak biomass and after combustion (250 °C) or pyrolysis (400 °C). Parent oak is primarily composed of cellulose-, lignin-, and resin-like compounds. Oak combusted at 250 °C contains condensed aromatic compounds with low H/C and O/C ratios while retaining compounds with high H/C and O/C ratios. The bimodal distribution of aromatic and aliphatic compounds observed in the combusted oak sample is attributed to incomplete thermal degradation of lignin and hemicellulose. Pyrolyzed oak constituents exhibit lower H/C and O/C ratios: approximately three-quarters of the identified species are aromatic. DAPPI FTICR MS results agree with bulk elemental composition as well as functional group distributions determined by elemental analysis and solid state (13)C NMR spectroscopy. Complete molecular characterization of biomass upon thermal transformation may provide insight into the biogeochemical cycles of biochar and future renewable energy sources, particularly for samples currently limited by solubility, separation, and sample preparation. PMID:22242739

  16. Determination of sterols using liquid chromatography with off-line surface-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Vrbková, Blanka; Roblová, Vendula; Yeung, Edward S; Preisler, Jan

    2014-09-01

    A new method, reversed phase liquid chromatography with off-line surface-assisted laser desorption/ionization mass spectrometry (RPLC-SALDI MS) for the determination of brassicasterol (BR), cholesterol (CH), stigmasterol (ST), campesterol (CA) and β-sitosterol (SI) in oil samples has been developed. The sample preparation consisted of alkaline saponification followed by extraction of the unsaponificable fraction with diethyl ether. The recovery of the sterols ranged from 91 to 95% with RSD less than 4%. Separation of the five major sterols on a C18 column using methanol-water gradient was achieved in about 10min. An on-line UV detector was employed for the initial sterol detection prior to effluent deposition using a laboratory-built spotter with 1:73 splitter. Off-line SALDI MS was then applied for mass determination/identification and quantification of the separated sterols. Ionization of the nonpolar analytes was achieved by silver ion cationization with silver nanoparticles used as the SALDI matrix providing limits of detection 12, 6 and 11fmol for CH, ST and SI, respectively. Because of the incorporated splitter, the effective limits of detection of the RPLC-SALDI MS analysis were 4, 3 and 4pmol (or 0.08, 0.06 and 0.08μg/mL) for CH, ST and SI, respectively. For quantification, 6-ketocholestanol (KE) was used as the internal standard. The method has been applied for the identification and quantification of sterols in olive, linseed and sunflower oil samples. The described off-line coupling of RPLC to SALDI MS represents an alternative to GC-MS for analysis of nonpolar compounds. PMID:25022478

  17. Identification and differentiation of the red ink entries of seals on document by laser desorption ionization mass spectrometry.

    PubMed

    Wang, Xiang-Feng; Zhang, Yun; Wu, Yao; Yu, Jing; Xie, Meng-Xia

    2014-03-01

    The establishment of approaches for the differentiation of the ink entries of seals on paper can provide evidence to authenticate the related documents and can play a key role in judicial expertise. The identification and discrimination method for 38 red ink entries of seals on paper has been investigated using laser desorption ionization mass spectrometry (LDI-MS). Six dye components for the ink pastes of seals, Scarlet powder (SP), Bronze Red C (BR), Fast Red R (FR), Basic Violet 3 (BV3), Pigment Red 22 (PR22) and Pigment Red 112 (PR112), have been identified by their LDI-MS spectra, and the results have been confirmed by electrospray ionization quadruple-time of flight mass spectrometry (QTOF-ESI-MS/MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES). The 38 ink entries were classified into six groups based on the presence or the absence of the pigments in their positive and negative LDI-MS spectra, and the discrimination power (DP) was calculated to be about 82%. The ink entries within each group were further differentiated from the relative peak areas (RPA) of the fragments for the pigments and the profile of their LDI-MS spectra, and thus the DP was increased to 98%. All the 38 ink entries could be discriminated (the DP was 100%), if including the contribution of unknown peaks. Compared with the results obtained by the FTIR and Raman methods, the established LDI-MS approach could provide more information of the dye components in the ink entries. The results showed that the developed LDI-MS method is powerful, sensitive and rapid and can directly differentiate the red ink entries of seals from paper substrates, thus offering a novel approach to judge the authenticity of documents.

  18. Two-Step Resonance-Enhanced Desorption Laser Mass Spectrometry for In Situ Analysis of Organic-Rich Environments

    NASA Technical Reports Server (NTRS)

    Getty, S. A.; Grubisic, A.; Uckert, K.; Li, X.; Cornish, T.; Cook, J. E.; Brinckerhoff, W. B.

    2016-01-01

    A wide diversity of planetary surfaces in the solar system represent high priority targets for in situ compositional and contextual analysis as part of future missions. The planned mission portfolio will inform our knowledge of the chemistry at play on Mars, icy moons, comets, and primitive asteroids, which can lead to advances in our understanding of the interplay between inorganic and organic building blocks that led to the evolution of habitable environments on Earth and beyond. In many of these environments, the presence of water or aqueously altered mineralogy is an important indicator of habitable environments that are present or may have been present in the past. As a result, the search for complex organic chemistry that may imply the presence of a feedstock, if not an inventory of biosignatures, is naturally aligned with targeted analyses of water-rich surface materials. Here we describe the two-step laser mass spectrometry (L2MS) analytical technique that has seen broad application in the study of organics in meteoritic samples, now demonstrated to be compatible with an in situ investigation with technique improvements to target high priority planetary environments as part of a future scientific payload. An ultraviolet (UV) pulsed laser is used in previous and current embodiments of laser desorption/ionization mass spectrometry (LDMS) to produce ionized species traceable to the mineral and organic composition of a planetary surface sample. L2MS, an advanced technique in laser mass spectrometry, is selective to the aromatic organic fraction of a complex sample, which can provide additional sensitivity and confidence in the detection of specific compound structures. Use of a compact two-step laser mass spectrometer prototype has been previously reported to provide specificity to key aromatic species, such as PAHs, nucleobases, and certain amino acids. Recent improvements in this technique have focused on the interaction between the mineral matrix and the

  19. Enzyme-coupled nanoparticles-assisted laser desorption ionization mass spectrometry for searching for low-mass inhibitors of enzymes in complex mixtures.

    PubMed

    Salwiński, Aleksander; Da Silva, David; Delépée, Raphaël; Maunit, Benoît

    2014-04-01

    In this report, enzyme-coupled magnetic nanoparticles (EMPs) were shown to be an effective affinity-based tool for finding specific interactions between enzymatic targets and the low-mass molecules in complex mixtures using classic MALDI-TOF apparatus. EMPs used in this work act as nonorganic matrix enabling ionization of small molecules without any interference in the low-mass range (enzyme-coupled nanoparticles-assisted laser desorption ionization MS, ENALDI MS) and simultaneously carry the superficial specific binding sites to capture inhibitors present in a studied mixture. We evaluated ENALDI approach in two complementary variations: 'ion fading' (IF-ENALDI), based on superficial adsorption of inhibitors and 'ion hunting' (IH-ENALDI), based on selective pre-concentration of inhibitors. IF-ENALDI was applied for two sets of enzyme-inhibitor pairs: tyrosinase-glabridin and trypsin-leupeptin and for the real plant sample: Sparrmannia discolor leaf and stem methanol extract. The efficacy of IH-ENALDI was shown for the pair of trypsin-leupeptin. Both ENALDI approaches pose an alternative for bioassay-guided fractionation, the common method for finding inhibitors in the complex mixtures.

  20. Enzyme-Coupled Nanoparticles-Assisted Laser Desorption Ionization Mass Spectrometry for Searching for Low-Mass Inhibitors of Enzymes in Complex Mixtures

    NASA Astrophysics Data System (ADS)

    Salwiński, Aleksander; Da Silva, David; Delépée, Raphaël; Maunit, Benoît

    2014-04-01

    In this report, enzyme-coupled magnetic nanoparticles (EMPs) were shown to be an effective affinity-based tool for finding specific interactions between enzymatic targets and the low-mass molecules in complex mixtures using classic MALDI-TOF apparatus. EMPs used in this work act as nonorganic matrix enabling ionization of small molecules without any interference in the low-mass range (enzyme-coupled nanoparticles-assisted laser desorption ionization MS, ENALDI MS) and simultaneously carry the superficial specific binding sites to capture inhibitors present in a studied mixture. We evaluated ENALDI approach in two complementary variations: `ion fading' (IF-ENALDI), based on superficial adsorption of inhibitors and `ion hunting' (IH-ENALDI), based on selective pre-concentration of inhibitors. IF-ENALDI was applied for two sets of enzyme-inhibitor pairs: tyrosinase-glabridin and trypsin-leupeptin and for the real plant sample: Sparrmannia discolor leaf and stem methanol extract. The efficacy of IH-ENALDI was shown for the pair of trypsin-leupeptin. Both ENALDI approaches pose an alternative for bioassay-guided fractionation, the common method for finding inhibitors in the complex mixtures.

  1. Determination of Macrolide Antibiotics Using Dispersive Liquid-Liquid Microextraction Followed by Surface-Assisted Laser Desorption/Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Chen, Kuan-Yu; Yang, Thomas C.; Chang, Sarah Y.

    2012-06-01

    A novel method for the determination of macrolide antibiotics using dispersive liquid-liquid microextraction coupled to surface-assisted laser desorption/ionization mass spectrometric detection was developed. Acetone and dichloromethane were used as the disperser solvent and extraction solvent, respectively. A mixture of extraction solvent and disperser solvent were rapidly injected into a 1.0 mL aqueous sample to form a cloudy solution. After the extraction, macrolide antibiotics were detected using surface-assisted laser desorption/ionization mass spectrometry (SALDI/MS) with colloidal silver as the matrix. Under optimum conditions, the limits of detection (LODs) at a signal-to-noise ratio of 3 were 2, 3, 3, and 2 nM for erythromycin (ERY), spiramycin (SPI), tilmicosin (TILM), and tylosin (TYL), respectively. This developed method was successfully applied to the determination of macrolide antibiotics in human urine samples.

  2. BioAerosol Mass Spectrometry: Reagentless Detection of Individual Airborne Spores and Other Bioagent Particles Based on Laser Desorption/Ionization Mass Spectrometry

    SciTech Connect

    Steele, Paul Thomas

    2004-09-01

    Better devices are needed for the detection of aerosolized biological warfare agents. Advances in the ongoing development of one such device, the BioAerosol Mass Spectrometry (BAMS) system, are described here in detail. The system samples individual, micrometer-sized particles directly from the air and analyzes them in real-time without sample preparation or use of reagents. At the core of the BAMS system is a dual-polarity, single-particle mass spectrometer with a laser based desorption and ionization (DI) system. The mass spectra produced by early proof-of-concept instruments were highly variable and contained limited information to differentiate certain types of similar biological particles. The investigation of this variability and subsequent changes to the DI laser system are described. The modifications have reduced the observed variability and thereby increased the usable information content in the spectra. These improvements would have little value without software to analyze and identify the mass spectra. Important improvements have been made to the algorithms that initially processed and analyzed the data. Single particles can be identified with an impressive level of accuracy, but to obtain significant reductions in the overall false alarm rate of the BAMS instrument, alarm decisions must be made dynamically on the basis of multiple analyzed particles. A statistical model has been developed to make these decisions and the resulting performance of a hypothetical BAMS system is quantitatively predicted. The predictions indicate that a BAMS system, with reasonably attainable characteristics, can operate with a very low false alarm rate (orders of magnitude lower than some currently fielded biodetectors) while still being sensitive to small concentrations of biological particles in a large range of environments. Proof-of-concept instruments, incorporating some of the modifications described here, have already performed well in independent testing.

  3. An experimental and modeling study of grain-scale uranium desorption from field-contaminated sediments and the potential influence of microporosity on mass-transfer

    NASA Astrophysics Data System (ADS)

    Stoliker, D.; Liu, C.; Kent, D. B.; Zachara, J. M.

    2012-12-01

    The aquifer below the 300-Area of the Hanford site (Richland, WA, USA) is plagued by a persistent plume of dissolved uranium (U(VI)) in excess of the Environmental Protection Agency drinking water maximum contamination level even after the removal of highly contaminated sediments. The aquifer sediments in the seasonally saturated lower vadose zone act as both a source and sink for uranium during stage changes in the nearby Columbia River. Diffusion limitation of uranium mass-transfer within these sediments has been cited as a potential cause of the plume's persistence. Equilibrium U(VI) sorption is a strong function of variable chemical conditions, especially carbonate, hydrogen, and uranyl ion activities. Field-contaminated sediments from the site require up to 1,000 hours to reach equilibrium in static batch reactors. Increases in U(VI) concentrations over longer time-scales result from changes in chemical conditions, which drive reactions with sediments that favor U(VI) desorption. Grain-scale U(VI) sorption/desorption rates are slow, likely owing to diffusion of U(VI) and other solutes through intra-granular pore domains. In order to improve understanding of the impact of intra-granular diffusion and chemical reactions controlling grain-scale U(VI) release, experiments were conducted on individual particle size fractions of a <8 mm composite of field-contaminated, lower vadose zone sediments. For each size fraction, equilibrium U(VI) sorption/desorption in static batch reactors was well-described by surface complexation models over a range of chemical conditions applicable to the field site. Desorption rates from individual size fractions in flow-through batch reactors, examined under a single set of constant chemical conditions with multiple stop-flow events, were similar for all size fractions <2 mm. Kinetic U(VI) desorption in flow-through batch reactors was modeled using a multi-rate surface complexation approach, where sorption/desorption rates were

  4. Differentiation of Raoultella ornithinolytica/planticola and Klebsiella oxytoca clinical isolates by matrix-assisted laser desorption/ionization-time of flight mass spectrometry.

    PubMed

    de Jong, Eefje; de Jong, Arjan S; Smidts-van den Berg, Nathalie; Rentenaar, Rob J

    2013-04-01

    Ninety-nine clinical isolates previously identified as Klebsiella oxytoca were evaluated using matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS). Eight isolates were identified as Raoultella spp., being 5 Raoultella spp. and 3 K. oxytoca, by 16S rRNA sequencing. These isolates were correctly identified by applying the 10% differential rule for the MALDI-TOF MS score values. This approach might be useful to discriminate Raoultella species from K. oxytoca.

  5. Analysis of Melamine, Cyanuric Acid, Ammelide, and Ammeline Using Matrix-Asssisted Laser Desorption Ionization/Time-of-Flight Mass Spectrometry (MALDI/TOFMS)

    SciTech Connect

    Campbell, James A.; Wunschel, David S.; Petersen, Catherine E.

    2007-12-01

    Melamine and cyanuric acid, two compounds connected to tainted pet food, have been analyzed using matrix-assisted laser desorption ionization/time-of-flight mass spectrometry. (M+H)+ ions were observed for melamine, ammelide, and ammeline under positive ion conditions with sinapinic acid as the matrix. With alpha-cyano-4-hydroxy-cinnamic acid as the matrix, a matrix-melamine complex was observed. (M-H)- was observed for cyanuric acid with sinapinic acid as the matrix.

  6. Identification of Non-diphtheriae Corynebacterium by Use of Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry

    PubMed Central

    Alatoom, Adnan A.; Cazanave, Charles J.; Cunningham, Scott A.; Ihde, Sherry M.

    2012-01-01

    We evaluated the Bruker Biotyper matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry for identification of 92 clinical isolates of Corynebacterium species in comparison to identification using rpoB or 16S rRNA gene sequencing. Eighty isolates (87%) yielded a score of ≥1.700, and all of these were correctly identified to the species level with the exception of Corynebacterium aurimucosum being misidentified as the closely related Corynebacterium minutissimum. PMID:22075579

  7. Influence of Culture Media on Detection of Carbapenem Hydrolysis by Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry.

    PubMed

    Ramos, Ana Carolina; Carvalhaes, Cecília Godoy; Cordeiro-Moura, Jhonatha Rodrigo; Rockstroh, Anna Carolina; Machado, Antonia Maria Oliveira; Gales, Ana Cristina

    2016-07-01

    In this study, we evaluated the influence of distinct bacterial growth media on detection of carbapenemase hydrolysis by matrix-assisted laser desorption ionization-time of flight mass spectrometry. False-negative results were observed for OXA-25-, OXA-26-, and OXA-72-producing Acinetobacter baumannii isolates grown on MacConkey agar medium. The other culture media showed 100% sensitivity and 100% specificity for detecting carbapenemase.

  8. Identification of Neisseria gonorrhoeae by the Bruker Biotyper Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry System Is Improved by a Database Extension.

    PubMed

    Schweitzer, Valentijn A; van Dam, Alje P; Hananta, I Putu Yuda; Schuurman, Rob; Kusters, Johannes G; Rentenaar, Rob J

    2016-04-01

    Identification ofNeisseria gonorrhoeaeby the Bruker matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) system may be affected by "B consistency categorization." A supplementary database of 17N. gonorrhoeaemain spectra was constructed. Twelve of 64N. gonorrhoeaeidentifications were categorized with B consistency, which disappeared using the supplementary database. Database extension did not result in misidentification ofNeisseria meningitidis. PMID:26763972

  9. Influence of Culture Media on Detection of Carbapenem Hydrolysis by Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry.

    PubMed

    Ramos, Ana Carolina; Carvalhaes, Cecília Godoy; Cordeiro-Moura, Jhonatha Rodrigo; Rockstroh, Anna Carolina; Machado, Antonia Maria Oliveira; Gales, Ana Cristina

    2016-07-01

    In this study, we evaluated the influence of distinct bacterial growth media on detection of carbapenemase hydrolysis by matrix-assisted laser desorption ionization-time of flight mass spectrometry. False-negative results were observed for OXA-25-, OXA-26-, and OXA-72-producing Acinetobacter baumannii isolates grown on MacConkey agar medium. The other culture media showed 100% sensitivity and 100% specificity for detecting carbapenemase. PMID:27076665

  10. A Simple and Safe Protocol for Preparing Brucella Samples for Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry Analysis

    PubMed Central

    Mesureur, Jennifer; Ranaldi, Sébastien; Monnin, Valérie; Girard, Victoria; Arend, Sandrine; Welker, Martin; O'Callaghan, David

    2015-01-01

    We describe a simple protocol to inactivate the biosafety level 3 (BSL3) pathogens Brucella prior to their analysis by matrix-assisted laser desorption ionization–time of flight mass spectrometry. This method is also effective for several other bacterial pathogens and allows storage, and eventually shipping, of inactivated samples; therefore, it might be routinely applied to unidentified bacteria, for the safety of laboratory workers. PMID:26582837

  11. Identification of Neisseria gonorrhoeae by the Bruker Biotyper Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry System Is Improved by a Database Extension

    PubMed Central

    Schweitzer, Valentijn A.; van Dam, Alje P.; Hananta, I Putu Yuda; Schuurman, Rob; Kusters, Johannes G.

    2016-01-01

    Identification of Neisseria gonorrhoeae by the Bruker matrix-assisted laser desorption ionization−time of flight mass spectrometry (MALDI-TOF MS) system may be affected by “B consistency categorization.” A supplementary database of 17 N. gonorrhoeae main spectra was constructed. Twelve of 64 N. gonorrhoeae identifications were categorized with B consistency, which disappeared using the supplementary database. Database extension did not result in misidentification of Neisseria meningitidis. PMID:26763972

  12. Determination of phospholipids in milk using a new phosphodiester stationary phase by liquid chromatography-matrix assisted desorption ionization mass spectrometry.

    PubMed

    Walczak, Justyna; Pomastowski, Paweł; Bocian, Szymon; Buszewski, Bogusław

    2016-02-01

    A methodology employing high performance liquid chromatography coupled with matrix-assisted laser desorption and ionization time-of-flight mass spectrometry has been utilized to determine the quality of phospholipid classes. Home-made phosphoester chemically bonded stationary phase containing diol, phosphate and octadecyl groups (Diol-P-C18) has been employed in the separation of polar lipids from milk. Each phospholipid fraction was collected manually and identified by MALDI-TOF MS.

  13. Combined Atomic Force Microscope-Based Topographical Imaging and Nanometer Scale Resolved Proximal Probe Thermal Desorption/Electrospray Ionization-Mass Spectrometry

    SciTech Connect

    Ovchinnikova, Olga S; Nikiforov, Maxim; Bradshaw, James A; Jesse, Stephen; Van Berkel, Gary J

    2011-01-01

    Nanometer scale proximal probe thermal desorption/electrospray ionization mass spectrometry (TD/ESI-MS) was demonstrated for molecular surface sampling of caffeine from a thin film using a 30 nm diameter nano-thermal analysis (nano-TA) probe tip in an atomic force microscope (AFM) coupled via a vapor transfer line and ESI interface to a MS detection platform. Using a probe temperature of 350 C and a spot sampling time of 30 s, conical desorption craters 250 nm in diameter and 100 nm deep were created as shown through subsequent topographical imaging of the surface within the same system. Automated sampling of a 5 x 2 array of spots, with 2 m spacing between spots, and real time selective detection of the desorbed caffeine using tandem mass spectrometry was also demonstrated. Estimated from the crater volume (~2x106 nm3), only about 10 amol (2 fg) of caffeine was liberated from each thermal desorption crater in the thin film. These results illustrate a relatively simple experimental setup and means to acquire in automated fashion sub-micrometer scale spatial sampling resolution and mass spectral detection of materials amenable to TD. The ability to achieve MS-based chemical imaging with 250 nm scale spatial resolution with this system is anticipated.

  14. Accurate mass fragment library for rapid analysis of pesticides on produce using ambient pressure desorption ionization with high-resolution mass spectrometry.

    PubMed

    Kern, Sara E; Lin, Lora A; Fricke, Frederick L

    2014-08-01

    U.S. food imports have been increasing steadily for decades, intensifying the need for a rapid and sensitive screening technique. A method has been developed that uses foam disks to sample the surface of incoming produce. This work provides complimentary information to the extensive amount of published pesticide fragmentation data collected using LCMS systems (Sack et al. Journal of Agricultural and Food Chemistry, 59, 6383-6411, 2011; Mol et al. Analytical and Bioanalytical Chemistry, 403, 2891-2908, 2012). The disks are directly analyzed using transmission-mode direct analysis in real time (DART) ambient pressure desorption ionization coupled to a high resolution accurate mass-mass spectrometer (HRAM-MS). In order to provide more certainty in the identification of the pesticides detected, a library of accurate mass fragments and isotopes of the protonated parent molecular ion (the [M+H]⁺) has been developed. The HRAM-MS is equipped with a quadrupole mass filter, providing the capability of "data-dependent" fragmentation, as opposed to "all -ion" fragmentation (where all of the ions enter a collision chamber and are fragmented at once). A temperature gradient for the DART helium stream and multiple collision energies were employed to detect and fragment 164 pesticides of varying chemical classes, sizes, and polarities. The accurate mass information of precursor ([M+H]⁺ ion) and fragment ions is essential in correctly identifying chemical contaminants on the surface of imported produce. Additionally, the inclusion of isotopes of the [M+H]⁺ in the database adds another metric to the confirmation process. The fragmentation data were collected using a Q-Exactive mass spectrometer and were added to a database used to process data collected with an Exactive mass spectrometer, an instrument that is more readily available for this screening application. The commodities investigated range from smooth-skinned produce such as apples to rougher surfaces like broccoli

  15. Accurate Mass Fragment Library for Rapid Analysis of Pesticides on Produce Using Ambient Pressure Desorption Ionization with High-Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Kern, Sara E.; Lin, Lora A.; Fricke, Frederick L.

    2014-08-01

    U.S. food imports have been increasing steadily for decades, intensifying the need for a rapid and sensitive screening technique. A method has been developed that uses foam disks to sample the surface of incoming produce. This work provides complimentary information to the extensive amount of published pesticide fragmentation data collected using LCMS systems (Sack et al. Journal of Agricultural and Food Chemistry, 59, 6383-6411, 2011; Mol et al. Analytical and Bioanalytical Chemistry, 403, 2891-2908, 2012). The disks are directly analyzed using transmission-mode direct analysis in real time (DART) ambient pressure desorption ionization coupled to a high resolution accurate mass-mass spectrometer (HRAM-MS). In order to provide more certainty in the identification of the pesticides detected, a library of accurate mass fragments and isotopes of the protonated parent molecular ion (the [M+H]+) has been developed. The HRAM-MS is equipped with a quadrupole mass filter, providing the capability of "data-dependent" fragmentation, as opposed to "all -ion" fragmentation (where all of the ions enter a collision chamber and are fragmented at once). A temperature gradient for the DART helium stream and multiple collision energies were employed to detect and fragment 164 pesticides of varying chemical classes, sizes, and polarities. The accurate mass information of precursor ([M+H]+ ion) and fragment ions is essential in correctly identifying chemical contaminants on the surface of imported produce. Additionally, the inclusion of isotopes of the [M+H]+ in the database adds another metric to the confirmation process. The fragmentation data were collected using a Q-Exactive mass spectrometer and were added to a database used to process data collected with an Exactive mass spectrometer, an instrument that is more readily available for this screening application. The commodities investigated range from smooth-skinned produce such as apples to rougher surfaces like broccoli. The

  16. The detection and mapping of the spatial distribution of insect defense compounds by desorption atmospheric pressure photoionization Orbitrap mass spectrometry.

    PubMed

    Rejšek, Jan; Vrkoslav, Vladimír; Hanus, Robert; Vaikkinen, Anu; Haapala, Markus; Kauppila, Tiina J; Kostiainen, Risto; Cvačka, Josef

    2015-07-30

    Many insects use chemicals synthesized in exocrine glands and stored in reservoirs to protect themselves. Two chemically defended insects were used as models for the development of a new rapid analytical method based on desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS). The distribution of defensive chemicals on the insect body surface was studied. Since these chemicals are predominantly nonpolar, DAPPI was a suitable analytical method. Repeatability of DAPPI-MS signals and effects related to non-planarity and roughness of samples were investigated using acrylic sheets uniformly covered with an analyte. After that, analytical figures of merit of the technique were determined. The spatial distribution of (E)-1-nitropentadec-1-ene, a toxic nitro compound synthesized by soldiers of the termite Prorhinotermes simplex, was investigated. Then, the spatial distribution of the unsaturated aldehydes (E)-hex-2-enal, (E)-4-oxohex-2-enal, (E)-oct-2-enal, (E,E)-deca-2,4-dienal and (E)-dec-2-enal was monitored in the stink bug Graphosoma lineatum. Chemicals present on the body surface were scanned along the median line of the insect from the head to the abdomen and vice versa, employing either the MS or MS(2) mode. In this fast and simple way, the opening of the frontal gland on the frons of termite soldiers and the position of the frontal gland reservoir, extending deep into the abdominal cavity, were localized. In the stink bug, the opening of the metathoracic scent glands (ostiole) on the ventral side of the thorax as well as the gland reservoir in the median position under the ventral surface of the anterior abdomen were detected and localized. The developed method has future prospects in routine laboratory use in life sciences. PMID:26320640

  17. Identification of Weissella species by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

    PubMed Central

    Lee, Meng-Rui; Tsai, Chia-Jung; Teng, Shih-Hua; Hsueh, Po-Ren

    2015-01-01

    Although some Weissella species play beneficial roles in food fermentation and in probiotic products, others such as Weissella confusa are emerging Gram-positive pathogens in immunocompromised hosts. Weissella species are difficult to identify by conventional biochemical methods and commercial automated systems and are easily misidentified as Lactobacillus and Leuconostoc species. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is increasingly being used for bacterial identification. Little, however, is known about the effectiveness of MALDI-TOF MS in identifying clinical isolates of Weissella to the species level. In this study, we evaluated whether the MALDI-TOF MS Bruker Biotyper system could accurately identify a total of 20 W. confusa and 2 W. cibaria blood isolates that had been confirmed by 16s rRNA sequencing analysis. The MALDI-TOF Biotyper system yielded no reliable identification results based on the current reference spectra for the two species (all score values <1.7). New W. confusa spectra were created by randomly selecting 3 W. confusa isolates and external validation was performed by testing the remaining 17 W. confusa isolates using the new spectra. The new main spectra projection (MSP) yielded reliable score values of >2 for all isolates with the exception of one (score value, 1.963). Our results showed that the MSPs in the current database are not sufficient for correctly identifying W. confusa or W. cibaria. Further studies including more Weissella isolates are warranted to further validate the performance of MALDI-TOF in identifying Weissella species. PMID:26594208

  18. Characterization of aromaticity in analogues of titan's atmospheric aerosols with two-step laser desorption ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Mahjoub, Ahmed; Schwell, Martin; Carrasco, Nathalie; Benilan, Yves; Cernogora, Guy; Szopa, Cyril; Gazeau, Marie-Claire

    2016-10-01

    The role of polycyclic aromatic hydrocarbons (PAH) and Nitrogen containing PAH (PANH) as intermediates of aerosol production in the atmosphere of Titan has been a subject of controversy for a long time. An analysis of the atmospheric emission band observed by the Visible and Infrared Mapping Spectrometer (VIMS) at 3.28 μm suggests the presence of neutral polycyclic aromatic species in the upper atmosphere of Titan. These molecules are seen as the counter part of negative and positive aromatics ions suspected by the Plasma Spectrometer onboard the Cassini spacecraft, but the low resolution of the instrument hinders any molecular speciation. In this work we investigate the specific aromatic content of Titan's atmospheric aerosols through laboratory simulations. We report here the selective detection of aromatic compounds in tholins, Titan's aerosol analogs, produced with a capacitively coupled plasma in a N2:CH4 95:5 gas mixture. For this purpose, Two-Step Laser Desorption Ionization Time-of-Flight Mass Spectrometry (L2DI-TOF-MS) technique is used to analyze the so produced analogs. This analytical technique is based on the ionization of molecules by Resonance Enhanced Multi-Photon Ionization (REMPI) using a λ=248 nm wavelength laser which is selective for aromatic species. This allows for the selective identification of compounds having at least one aromatic ring. Our experiments show that tholins contain a trace amount of small PAHs with one to three aromatic rings. Nitrogen containing PAHs (PANHs) are also detected as constituents of tholins. Molecules relevant to astrobiology are detected as is the case of the substituted DNA base adenine.

  19. The detection and mapping of the spatial distribution of insect defense compounds by desorption atmospheric pressure photoionization Orbitrap mass spectrometry.

    PubMed

    Rejšek, Jan; Vrkoslav, Vladimír; Hanus, Robert; Vaikkinen, Anu; Haapala, Markus; Kauppila, Tiina J; Kostiainen, Risto; Cvačka, Josef

    2015-07-30

    Many insects use chemicals synthesized in exocrine glands and stored in reservoirs to protect themselves. Two chemically defended insects were used as models for the development of a new rapid analytical method based on desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS). The distribution of defensive chemicals on the insect body surface was studied. Since these chemicals are predominantly nonpolar, DAPPI was a suitable analytical method. Repeatability of DAPPI-MS signals and effects related to non-planarity and roughness of samples were investigated using acrylic sheets uniformly covered with an analyte. After that, analytical figures of merit of the technique were determined. The spatial distribution of (E)-1-nitropentadec-1-ene, a toxic nitro compound synthesized by soldiers of the termite Prorhinotermes simplex, was investigated. Then, the spatial distribution of the unsaturated aldehydes (E)-hex-2-enal, (E)-4-oxohex-2-enal, (E)-oct-2-enal, (E,E)-deca-2,4-dienal and (E)-dec-2-enal was monitored in the stink bug Graphosoma lineatum. Chemicals present on the body surface were scanned along the median line of the insect from the head to the abdomen and vice versa, employing either the MS or MS(2) mode. In this fast and simple way, the opening of the frontal gland on the frons of termite soldiers and the position of the frontal gland reservoir, extending deep into the abdominal cavity, were localized. In the stink bug, the opening of the metathoracic scent glands (ostiole) on the ventral side of the thorax as well as the gland reservoir in the median position under the ventral surface of the anterior abdomen were detected and localized. The developed method has future prospects in routine laboratory use in life sciences.

  20. Microorganisms direct identification from blood culture by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Ferreira, L; Sánchez-Juanes, F; Porras-Guerra, I; García-García, M I; García-Sánchez, J E; González-Buitrago, J M; Muñoz-Bellido, J L

    2011-04-01

    Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) allows a fast and reliable bacterial identification from culture plates. Direct analysis of clinical samples may increase its usefulness in samples in which a fast identification of microorganisms can guide empirical treatment, such as blood cultures (BC). Three hundred and thirty BC, reported as positive by the automated BC incubation device, were processed by conventional methods for BC processing, and by a fast method based on direct MALDI-TOF MS. Three hundred and eighteen of them yield growth on culture plates, and 12 were false positive. The MALDI-TOF MS-based method reported that no peaks were found, or the absence of a reliable identification profile, in all these false positive BC. No mixed cultures were found. Among these 318 BC, we isolated 61 Gram-negatives (GN), 239 Gram-positives (GP) and 18 fungi. Microorganism identifications in GN were coincident with conventional identification, at the species level, in 83.3% of BC and, at the genus level, in 96.6%. In GP, identifications were coincident with conventional identification in 31.8% of BC at the species level, and in 64.8% at the genus level. Fungaemia was not reliably detected by MALDI-TOF. In 18 BC positive for Candida species (eight C. albicans, nine C. parapsilosis and one C. tropicalis), no microorganisms were identified at the species level, and only one (5.6%) was detected at the genus level. The results of the present study show that this fast, MALDI-TOF MS-based method allows bacterial identification directly from presumptively positive BC in a short time (<30 min), with a high accuracy, especially when GN bacteria are involved.

  1. Identification of Acinetobacter Species Using Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry

    PubMed Central

    Jeong, Seri; Hong, Jun Sung; Kim, Jung Ok; Kim, Keon-Han; Lee, Woonhyoung; Bae, Il Kwon; Lee, Kyungwon

    2016-01-01

    Background Acinetobacter baumannii has a greater clinical impact and exhibits higher antimicrobial resistance rates than the non-baumannii Acinetobacter species. Therefore, the correct identification of Acinetobacter species is clinically important. Matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry (MS) has recently become the method of choice for identifying bacterial species. The purpose of this study was to evaluate the ability of MALDI-TOF MS (Bruker Daltonics GmbH, Germany) in combination with an improved database to identify various Acinetobacter species. Methods A total of 729 Acinetobacter clinical isolates were investigated, including 447 A. baumannii, 146 A. nosocomialis, 78 A. pittii, 18 A. ursingii, 9 A. bereziniae, 9 A. soli, 4 A. johnsonii, 4 A. radioresistens, 3 A. gyllenbergii, 3 A. haemolyticus, 2 A. lwoffii, 2 A. junii, 2 A. venetianus, and 2 A. genomospecies 14TU. After 212 isolates were tested with the default Bruker database, the profiles of 63 additional Acinetobacter strains were added to the default database, and 517 isolates from 32 hospitals were assayed for validation. All strains in this study were confirmed by rpoB sequencing. Results The addition of the 63 Acinetobacter strains' profiles to the default Bruker database increased the overall concordance rate between MALDI-TOF MS and rpoB sequencing from 69.8% (148/212) to 100.0% (517/517). Moreover, after library modification, all previously mismatched 64 Acinetobacter strains were correctly identified. Conclusions MALDI-TOF MS enables the prompt and accurate identification of clinically significant Acinetobacter species when used with the improved database. PMID:27139605

  2. Distinctive Glycerophospholipid Profiles of Human Seminoma and Adjacent Normal Tissues by Desorption Electrospray Ionization Imaging Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Masterson, Timothy A.; Dill, Allison L.; Eberlin, Livia S.; Mattarozzi, Monica; Cheng, Liang; Beck, Stephen D. W.; Bianchi, Federica; Cooks, R. Graham

    2011-08-01

    Desorption electrospray ionization mass spectrometry (DESI-MS) has been successfully used to discriminate between normal and cancerous human tissue from different anatomical sites. On the basis of this, DESI-MS imaging was used to characterize human seminoma and adjacent normal tissue. Seminoma and adjacent normal paired human tissue sections (40 tissues) from 15 patients undergoing radical orchiectomy were flash frozen in liquid nitrogen and sectioned to 15 μm thickness and thaw mounted to glass slides. The entire sample was two-dimensionally analyzed by the charged solvent spray to form a molecular image of the biological tissue. DESI-MS images were compared with formalin-fixed, hematoxylin and eosin (H&E) stained slides of the same material. Increased signal intensity was detected for two seminolipids [seminolipid (16:0/16:0) and seminolipid (30:0)] in the normal tubule testis tissue; these compounds were undetectable in seminoma tissue, as well as from the surrounding fat, muscle, and blood vessels. A glycerophosphoinositol [PI(18:0/20:4)] was also found at increased intensity in the normal testes tubule tissue when compared with seminoma tissue. Ascorbic acid (i.e., vitamin C) was found at increased amounts in seminoma tissue when compared with normal tissue. DESI-MS analysis was successfully used to visualize the location of several types of molecules across human seminoma and normal tissues. Discrimination between seminoma and adjacent normal testes tubules was achieved on the basis of the spatial distributions and varying intensities of particular lipid species as well as ascorbic acid. The increased presence of ascorbic acid within seminoma compared with normal seminiferous tubules was previously unknown.

  3. Differentiation of Microbial Species and Strains in Coculture Biofilms by Multivariate Analysis of Laser Desorption Postionization Mass Spectra

    SciTech Connect

    University of Illinois at Chicago; Montana State University; Bhardwaj, Chhavi; Cui, Yang; Hofstetter, Theresa; Liu, Suet Yi; Bernstein, Hans C.; Carlson, Ross P.; Ahmed, Musahid; Hanley, Luke

    2013-04-01

    7.87 to 10.5 eV vacuum ultraviolet (VUV) photon energies were used in laser desorption postionization mass spectrometry (LDPI-MS) to analyze biofilms comprised of binary cultures of interacting microorganisms. The effect of photon energy was examined using both tunable synchrotron and laser sources of VUV radiation. Principal components analysis (PCA) was applied to the MS data to differentiate species in Escherichia coli-Saccharomyces cerevisiae coculture biofilms. PCA of LDPI-MS also differentiated individual E. coli strains in a biofilm comprised of two interacting gene deletion strains, even though these strains differed from the wild type K-12 strain by no more than four gene deletions each out of approximately 2000 genes. PCA treatment of 7.87 eV LDPI-MS data separated the E. coli strains into three distinct groups two ?pure? groups and a mixed region. Furthermore, the ?pure? regions of the E. coli cocultures showed greater variance by PCA when analyzed by 7.87 eV photon energies than by 10.5 eV radiation. Comparison of the 7.87 and 10.5 eV data is consistent with the expectation that the lower photon energy selects a subset of low ionization energy analytes while 10.5 eV is more inclusive, detecting a wider range of analytes. These two VUV photon energies therefore give different spreads via PCA and their respective use in LDPI-MS constitute an additional experimental parameter to differentiate strains and species.

  4. Neutral loss analysis of amino acids by desorption electrospray ionization using an unmodified tandem quadrupole mass spectrometer.

    PubMed

    Corso, Gaetano; Paglia, Giuseppe; Garofalo, Daniela; D'Apolito, Oceania

    2007-01-01

    A new method to analyze free amino acids using desorption electrospray ionization (DESI) has been implemented. The method is based on the neutral loss mode determination of underivatized amino acids using a tandem quadrupole mass spectrometer equipped with an unmodified atmospheric interface. Qualitative and quantitative optimization of DESI parameters, including ESI voltage, solvent flow rate, angle of collection and incidence, gas flow and temperatures, was performed for amino acids detection. The parameters for DESI analysis were evaluated using a mixture of valine, leucine, methionine, phenylalanine and tyrosine standards. A few microliters of this mixture were deposited on a slide, dried and analyzed at a flow rate of 2 microL/min. The optimal ionization response was obtained using laboratory glass slides and an equivalent solution of water/methanol doped with 2% of formic acid. The method specificity was evaluated by comparing product ion spectra and neutral loss analysis of amino acids obtained either by DESI or by electrospray ionization flow injection analysis (ESI-FIA). To evaluate the quantitative response on amino acids analyzed by DESI, calibration curves were performed on amino acid standard solutions spiked with a fixed amount of labelled amino acids. The method was also employed to analyze free amino acids from blood spots, after a rapid solvent extraction without other sample pretreatment, from positive and negative subjects. The method enables one to analyze biological samples and to discriminate healthy subjects from patients affected by inherited metabolic diseases. The intrinsic high-throughput analysis of DESI represents an opportunity, because of its potential application in clinical chemistry, for the expanded screening of some inborn errors of metabolism.

  5. Using Surface-Assisted Laser Desorption/Ionization Mass Spectrometry to Detect ss- and ds-Oligodeoxynucleotides

    NASA Astrophysics Data System (ADS)

    Chen, Wen-Tsen; Huang, Ming-Feng; Chang, Huan-Tsung

    2013-06-01

    We applied surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) with HgTe nanostructures as the matrix for the detection of single- and double-stranded oligodeoxynucleotides (ss-ODNs and ds-ODNs). The concentrations of surfactant and additives (metal ions, an amine) and the pH and ionic strength of the sample matrix played significantly different roles in the detection of ss- and ds-ODNs with various sequences. In the presence of Brij 76 (1.5 %), Hg2+ (7.5 μM), and cadaverine (10 μM) at pH 5.0, this SALDI-MS approach allowed the simultaneous detection of T15, T20, T33, and T40, with limits of detection at the femtomole-to-picomole level and sample-to-sample intensity variation <23 %. In the presence of Ag+ (1 μM) and cadaverine (10 μM) at pH 7.0, this technique allowed the detection of randomly sequenced ss- and ds-ODNs at concentrations down to the femtomole level. To the best of our knowledge, this paper is the first to report the detection of ss-ODNs (up to 50-mer) and ds-ODNs (up to 30 base pairs) through the combination of SALDI-MS with HgTe nanostructures as matrices. We demonstrated the practicality of this approach through analysis of a single nucleotide polymorphism that determines the fate of the valine residue in the β-globin of sickle cell megaloblasts.

  6. Three-dimensional imaging of lipids and metabolites in tissues by nanospray desorption electrospray ionization mass spectrometry

    PubMed Central

    Lanekoff, Ingela; Burnum-Johnson, Kristin; Thomas, Mathew; Cha, Jeeyeon; Dey, Sudhansu K.; Yang, Pengxiang; Prieto Conaway, Maria C.

    2016-01-01

    Three-dimensional (3D) imaging of tissue sections is a new frontier in mass spectrometry imaging (MSI). Here, we report on fast 3D imaging of lipids and metabolites associated with mouse uterine decidual cells and embryo at the implantation site on day 6 of pregnancy. 2D imaging of 16–20 serial tissue sections deposited on the same glass slide was performed using nanospray desorption electrospray ionization (nano-DESI)—an ambient ionization technique that enables sensitive localized analysis of analytes on surfaces without special sample pretreatment. In this proof-of-principle study, nano-DESI was coupled to a high-resolution Q-Exactive instrument operated at high repetition rate of >5 Hz with moderate mass resolution of 35,000 (m/Δm at m/z 200), which enabled acquisition of the entire 3D image with a spatial resolution of ~150 μm in less than 4.5 h. The results demonstrate localization of acetylcholine in the primary decidual zone (PDZ) of the implantation site throughout the depth of the tissue examined, indicating an important role of this signaling molecule in decidualization. Choline and phosphocholine—metabolites associated with cell growth— are enhanced in the PDZ and abundant in other cellular regions of the implantation site. Very different 3D distributions were obtained for fatty acids (FA), oleic acid and linoleic acid (FA 18:1 and FA 18:2), differing only by one double bond. Localization of FA 18:2 in the PDZ indicates its important role in decidualization while FA 18:1 is distributed more evenly throughout the tissue. In contrast, several lysophosphatidylcholines (LPC) observed in this study show donut-like distributions with localization around the PDZ. Complementary distributions with minimal overlap were observed for LPC 18:0 and FA 18:2 while the 3D image of the potential precursor phosphatidylcholine 36:2 (PC 36:2) showed a significant overlap with both LPC 18:0 and FA 18:2. PMID:25395201

  7. Three-Dimensional Imaging of Lipids and Metabolites in Tissues by Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Lanekoff, Ingela T.; Burnum-Johnson, Kristin E.; Thomas, Mathew; Cha, Jeeyeon; Dey, Sudhansu K.; yang, Pengxiang; Prieto, Mari; Laskin, Julia

    2015-03-01

    Abstract Three-dimensional (3D) imaging of tissue sections is a new frontier in mass spectrometry imaging (MSI). Here we report on fast 3D imaging of lipids and metabolites associated with mouse uterine decidual cells and embryo at the implantation site on day 6 of pregnancy. 2D imaging of 16-20 serial tissue sections deposited on the same glass slide was performed using nanospray desorption electrospray ionization (nano-DESI) – an ambient ionization technique that enables sensitive localized analysis of analytes on surfaces without special sample pre-treatment. In this proof-of-principle study, nano-DESI was coupled to a high-resolution Q-Exactive instrument operated at high repetition rate of >5 Hz with moderate mass resolution of 35,000 (m/Δm at m/z 200), which enabled acquisition of the entire 3D image with a spatial resolution of ~150 μm in less than 4.5 hours. The results demonstrate localization of acetylcholine in the primary decidual zone (PDZ) of the implantation site throughout the depth of the tissue examined, indicating an important role of this signaling molecule in decidualization. Choline and phosphocholine – metabolites associated with cell growth – are enhanced in the PDZ and abundant in other cellular regions of the implantation site. Very different 3D distributions were obtained for fatty acids (FA), oleic acid and linoleic acid (FA 18:1 and FA 18:2), differing only by one double bond. Localization of FA 18:2 in the PDZ indicates its important role in decidualization while FA 18:1 is distributed more evenly throughout the tissue. In contrast, several lysophosphatidylcholines (LPC) observed in this study show donut-like distributions with localization around the PDZ. Complementary distributions with minimal overlap were observed for LPC 18:0 and FA 18:2 while the 3D image of the potential precursor phosphatidylcholine (PC 36:2) showed a significant overlap with both LPC 18:0 and FA 18:2.

  8. In Situ Probing of Cholesterol in Astrocytes at the Single Cell Level using Laser Desorption Ionization Mass Spectrometric Imaging with Colloidal Silver

    SciTech Connect

    Perdian, D.C.; Cha, Sangwon; Oh, Jisun; Sakaguchi, Donald S.; Yeung, Edward S.; and Lee, Young Jin

    2010-03-18

    Mass spectrometric imaging has been utilized to localize individual astrocytes and to obtain cholesterol populations at the single-cell level in laser desorption ionization (LDI) with colloidal silver. The silver ion adduct of membrane-bound cholesterol was monitored to detect individual cells. Good correlation between mass spectrometric and optical images at different cell densities indicates the ability to perform single-cell studies of cholesterol abundance. The feasibility of quantification is confirmed by the agreement between the LDI-MS ion signals and the results from a traditional enzymatic fluorometric assay. We propose that this approach could be an effective tool to study chemical populations at the cellular level.

  9. A novel type of matrix for surface-assisted laser desorption-ionization mass spectrometric detection of biomolecules using metal-organic frameworks.

    PubMed

    Fu, Chien-Ping; Lirio, Stephen; Liu, Wan-Ling; Lin, Chia-Her; Huang, Hsi-Ya

    2015-08-12

    A 3D metal-organic framework (MOF) nanomaterial as matrix for surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) and tandem mass spectrometry (MS/MS) was developed for the analysis of complex biomolecules. Unlike other nanoparticle matrices, this MOF nanomaterial does not need chemical modification prior to use. An exceptional signal reproducibility as well as very low background interferences in analyzing mono-/di-saccharides, peptides and complex starch digests demonstrate its high potential for biomolecule assays, especially for small molecules. PMID:26320964

  10. Identification of arsenobetaine in sole, lemon sole, flounder, dab, crab and shrimps by field desorption and fast atom bombardment mass spectrometry

    SciTech Connect

    Luten, J.B.; Riekwel-Booy, G.; Greef, M.C.; de Brauw, I.N.

    1983-01-01

    Organo-arsenic has been isolated from sole, lemon sole, flounder, dab, crab and shrimps by extraction or ion-exchange in combination with thin-layer chromatography. An alkaline digestion of the samples, followed by a reduction with sodiumborohydride leads to the formation of trimethylarsine. Field desorption mass spectrometry (FDMS) can be used to identify arsenobetaine in the isolates. Sufficient purification by thin-layer chromatography is found to be a prerequisite for the detection of a protonated molecular ion of arsenobetaine. If this situation is not met acid enchanced FDMS or Fast Atom Bombardment mass spectrometry in high resolution can be used successfully.

  11. A technique for obtaining matrix-assisted laser desorption/ionization time-of-flight mass spectra of poorly soluble and insoluble aromatic polyamides.

    PubMed

    Gies, Anthony P; Nonidez, William K

    2004-04-01

    Wet grinding methods for obtaining matrix-assisted laser desorption/ionization time-of-flight mass spectra of poorly soluble and insoluble low molecular mass oligomers (<4600 Da) of Nomex and Kevlar are described. Optimum conditions for sample preparation are given along with a detailed analysis of the spectra obtained. Two matrix materials were employed in this analysis, 1,8-dihydroxyanthrone (dithranol) and 3-aminoquinoline with potassium trifluoroacetate used as the cationizing agent. The spectra obtained in this study are sensitive to the matrix, molar mixing ratios of matrix/polymer/cationizing agent, and the sample preparation method. PMID:15053662

  12. Detailed investigation on the possibility of nanoparticles of various metal elements for surface-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Yonezawa, Tetsu; Kawasaki, Hideya; Tarui, Akira; Watanabe, Takehiro; Arakawa, Ryuichi; Shimada, Toshihiro; Mafuné, Fumitaka

    2009-03-01

    In this paper, we describe systematic detailed considerations of the feasibility of using various metal nanoparticles for organic-matrix-free surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). In order to avoid the influence of organic molecules on the nanoparticles, stabilizer-free bare nanoparticles of Ag, Au, Cu and Pt were prepared by laser ablation. Although all metal nanoparticles absorbed N(2) laser light (337 nm) energy, the performance of desorption/ionization of a representative peptide, angiotensin I, strongly depended on the metal element. Citrate buffer was used as a proton source; it reduced the amount of alkali cation adducts present. Then, protonated molecules of analytes predominated in the mass spectra when Au and Pt nanoparticles were used. Pt nanoparticles showed the highest performance in SALDI-MS, owing to their smaller heat conductivity and higher melting temperature. The selective desorption of a cationic surfactant with longer alkyl chains and a peptide with methionine was also observed. PMID:19276588

  13. In situ identification of organic components of ink used in books from the 1900s by atmospheric pressure matrix assisted laser desorption ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Giurato, Laura; Candura, Andrea; Grasso, Giuseppe; Spoto, Giuseppe

    2009-11-01

    This paper describes the use of atmospheric pressure/matrix assisted laser desorption ionization-mass spectrometry (AP/MALDI-MS) as a spatially resolved analytical technique for the study of organic components of inks used to print coloured parts of ancient books. The possibility to operate at atmospheric pressure makes MALDI-MS a new in situ micro-destructive diagnostic tool suitable for analysing samples in air, simplifying the investigation of the organic components of artistic and archaeological objects. In this work, several organic dyes and pigments were identified in situ by analysing different coloured areas of books printed in the years 1911 and 1920. The detected colouring materials, which were available since the 1890s, were often identified as a mixture, confirming the typical procedures used in the lithographic printing processes. The matrix deposition and the laser desorption process did not cause visible alteration of the sample surface.

  14. Determination of seven pyrethroids biocides and their synergist in indoor air by thermal-desorption gas chromatography/mass spectrometry after sampling on Tenax TA ® passive tubes.

    PubMed

    Raeppel, Caroline; Appenzeller, Brice M; Millet, Maurice

    2015-01-01

    A method coupling thermal desorption and gas chromatography/mass spectrometry (GC/MS) was developed for the simultaneous determination of 7 pyrethroids (allethrin, bifenthrin, cyphenothrin, imiprothrin, permethrin, prallethrin and tetramethrin) and piperonyl butoxide adsorbed on Tenax TA(®) passive samplers after exposure in indoor air. Thermal desorption was selected as it permits efficient and rapid extraction without solvent used together with a good sensitivity. Detection (S/N>3) and quantification (S/N>10) limits varied between 0.001 ng and 2.5 ng and between 0.005 and 10 ng respectively with a reproducibility varied between 14% (bifenthrin) and 39% (permethrin). The method was used for the comparison indoor air contamination after low-pressure spraying and fumigation application in a rubbish chute situated in the basement of a building.

  15. Rapid on-site detection of explosives on surfaces by ambient pressure laser desorption and direct inlet single photon ionization or chemical ionization mass spectrometry.

    PubMed

    Ehlert, S; Hölzer, J; Rittgen, J; Pütz, M; Schulte-Ladbeck, R; Zimmermann, R

    2013-09-01

    Considering current security issues, powerful tools for detection of security-relevant substances such as traces of explosives and drugs/drug precursors related to clandestine laboratories are required. Especially in the field of detection of explosives and improvised explosive devices, several relevant compounds exhibit a very low vapor pressure. Ambient pressure laser desorption is proposed to make these substances available in the gas phase for the detection by adapted mass spectrometers or in the future with ion-mobility spectrometry as well. In contrast to the state-of-the-art thermal desorption approach, by which the sample surface is probed for explosive traces by a wipe pad being transferred to a thermal desorber unit, by the ambient pressure laser desorption approach presented here, the sample is directly shockwave ablated from the surface. The laser-dispersed molecules are sampled by a heated sniffing capillary located in the vicinity of the ablation spot into the mass analyzer. This approach has the advantage that the target molecules are dispersed more gently than in a thermal desorber unit where the analyte molecules may be decomposed by the thermal intake. In the technical realization, the sampling capillary as well as the laser desorption optics are integrated in the tip of an endoscopic probe or a handheld sampling module. Laboratory as well as field test scenarios were performed, partially in cooperation with the Federal Criminal Police Office (Bundeskriminalamt, BKA, Wiesbaden, Germany), in order to demonstrate the applicability for various explosives, drugs, and drug precursors. In this work, we concentrate on the detection of explosives. A wide range of samples and matrices have been investigated successfully.

  16. Hydrogen sulphide in human nasal air quantified using thermal desorption and selected ion flow tube mass spectrometry.

    PubMed

    Wondimu, Taddese; Wang, Rui; Ross, Brian

    2014-09-01

    The discovery that hydrogen sulphide (H2S) acts as a gasotransmitter when present at very low concentrations (sub-parts per billion (ppbv)) has resulted in the need to quickly quantify trace amounts of the gas in complex biological samples. Selected ion flow tube mass spectrometry (SIFT-MS) is capable of real-time quantification of H2S but many SIFT-MS instruments lack sufficient sensitivity for this application. In this study we investigate the utility of combining thermal desorption with SIFT-MS for quantifying H2S in the 0.1-1 ppbv concentration range. Human orally or nasally derived breath, and background ambient air, were collected in sampling bags and dried by passing through CaCl2 and H2S pre-concentrated using a sorbent trap optimised for the capture of this gas. The absorbed H2S was then thermally desorbed and quantified by SIFT-MS. H2S concentrations in ambient air, nasal breath and oral breath collected from 10 healthy volunteers were 0.12  ±  0.02 (mean ± SD), 0.40  ±  0.11 and 3.1  ±  2.5 ppbv respectively, and in the oral cavity H2S, quantified by SIFT-MS without pre-concentration, was present at 13.5  ±  8.6 ppbv. The oral cavity H2S correlates well with oral breath H2S but not with nasal breath H2S, suggesting that oral breath H2S derives mainly from the oral cavity but nasal breath is likely pulmonary in origin. The successful quantification of such low concentrations of H2S in nasal air using a rapid analytical procedure paves the way for the straightforward analysis of H2S in breath and may assist in elucidating the role that H2S plays in biological systems.

  17. Soft-landing ion mobility of silver clusters for small-molecule matrix-assisted laser desorption ionization mass spectrometry and imaging of latent fingerprints.

    PubMed

    Walton, Barbara L; Verbeck, Guido F

    2014-08-19

    Matrix-assisted laser desorption ionization (MALDI) imaging is gaining popularity, but matrix effects such as mass spectral interference and damage to the sample limit its applications. Replacing traditional matrices with silver particles capable of equivalent or increased photon energy absorption from the incoming laser has proven to be beneficial for low mass analysis. Not only can silver clusters be advantageous for low mass compound detection, but they can be used for imaging as well. Conventional matrix application methods can obstruct samples, such as fingerprints, rendering them useless after mass analysis. The ability to image latent fingerprints without causing damage to the ridge pattern is important as it allows for further characterization of the print. The application of silver clusters by soft-landing ion mobility allows for enhanced MALDI and preservation of fingerprint integrity.

  18. Determination of volatile organic compounds in different microenvironments by multibed adsorption and short-path thermal desorption followed by gas chromatographic-mass spectrometric analysis.

    PubMed

    Kuntasal, Oznur Oğuz; Karman, Deniz; Wang, Daniel; Tuncel, Semra G; Tuncel, Gürdal

    2005-12-16

    A multiphase assurance approach was developed for the accurate and precise determination of volatile organic compounds (VOCs) in different microenvironments. This approach includes (i) development of a method including adsorption of VOCs onto a multisorbent media followed by short-path thermal desorption (SPTD) pre-concentration and gas chromatography (GC) coupled to a mass spectrometry (MS) quantification, (ii) validation of the sampling and analytical method and (iii) validation of the data using a multidimensional procedure. Tenax TA and Carbopack B sorbent combinations were used to collect 102 individual VOCs ranging from C5 to C12. Method parameters including thermal desorption temperature, desorption time and cryofocusing temperature were optimized. The average recoveries and method detection limits (MDL) for the target analytes were in the range 80-100% and 0.01-0.14 ppbv, respectively. The method also showed good linearity (R2 > 0.99) and precision (<8%) values. Validation of the method was performed under real environmental conditions at a gas station, in an office and a residential household to examine the influence of variation in meteorological conditions such as temperature and relative humidity and a wide range of VOC concentrations. The sampling and analytical method resulted in successful determination of VOC in different microenvironments. Finally, validation of the data was performed by assessing fingerprint and time series plots and correlation matrices together with meteorological parameters such as mixing height, wind speed and temperature. The data validation procedure provided detection of both faulty data and air pollution episodes.

  19. Analysis of the volatile organic matter of engine piston deposits by direct sample introduction thermal desorption gas chromatography/mass spectrometry.

    PubMed

    Diaby, M; Kinani, S; Genty, C; Bouchonnet, S; Sablier, M; Le Negrate, A; El Fassi, M

    2009-12-01

    This article establishes an alternative method for the characterization of volatiles organic matter (VOM) contained in deposits of the piston first ring grooves of diesel engines using a ChromatoProbe direct sample introduction (DSI) device coupled to gas chromatography/mass spectrometry (GC/MS) analysis. The addition of an organic solvent during thermal desorption leads to an efficient extraction and a good chromatographic separation of extracted products. The method was optimized investigating the effects of several solvents, the volume added to the solid sample, and temperature programming of the ChromatoProbe DSI device. The best results for thermal desorption were found using toluene as an extraction solvent and heating the programmable temperature injector from room temperature to 300 degrees C with a temperature step of 105 degrees C. With the use of the optimized thermal desorption conditions, several components have been positively identified in the volatile fraction of the deposits: aromatics, antioxidants, and antioxidant degradation products. Moreover, this work highlighted the presence of diesel fuel in the VOM of the piston deposits and gave new facts on the absence of the role of diesel fuel in the deposit formation process. Most importantly, it opens the possibility of quickly performing the analysis of deposits with small amounts of samples while having a good separation of the volatiles. PMID:19894696

  20. Depth profiling of inks in authentic and counterfeit banknotes by electrospray laser desorption ionization/mass spectrometry.

    PubMed

    Kao, Yi-Ying; Cheng, Sy-Chyi; Cheng, Chu-Nian; Shiea, Jentaie

    2016-01-01

    Electrospray laser desorption ionization is an ambient ionization technique that generates neutrals via laser desorption and ionizes those neutrals in an electrospray plume and was utilized to characterize inks in different layers of copy paper and banknotes of various currencies. Depth profiling of inks was performed on overlapping color bands on copy paper by repeatedly scanning the line with a pulsed laser beam operated at a fixed energy. The molecules in the ink on a banknote were desorbed by irradiating the banknote surface with a laser beam operated at different energies, with results indicating that different ions were detected at different depths. The analysis of authentic $US100, $100 RMB and $1000 NTD banknotes indicated that ions detected in 'color-shifting' and 'typography' regions were significantly different. Additionally, the abundances of some ions dramatically changed with the depth of the aforementioned regions. This approach was used to distinguish authentic $1000 NTD banknotes from counterfeits. Copyright © 2015 John Wiley & Sons, Ltd.

  1. Formation of aluminium, aluminium nitride and nitrogen clusters via laser ablation of nano aluminium nitride. Laser Desorption Ionisation and Matrix-Assisted Laser Desorption Ionisation Time-of-Flight Mass Spectrometry.

    PubMed

    Panyala, Nagender Reddy; Prysiazhnyi, Vadym; Slavíček, Pavel; Černák, Mirko; Havel, Josef

    2011-06-30

    Laser Desorption Ionisation (LDI) and Matrix-Assisted Laser Desorption Ionisation (MALDI) Time-of-Flight Mass Spectrometry (TOFMS) were used to study the pulsed laser ablation of aluminium nitride (AlN) nano powder. The formation of Al(m)(+) (m=1-3), N(n)(+) (n=4, 5), AlN(n)(+) (n=1-5, 19, 21), Al(m)N(+) (m=2-3), Al(3)N(2)(+), Al(9)N(n)(+) (n=5, 7, 9, 11 and 15), Al(11)N(n)(+) (n=4, 6, 10, 12, 19, 21, 23, and 25), and Al(13)N(n)(+) (n=25, 31, 32, 33, 34, 35, and 36) clusters was detected in positive ion mode. Similarly, Al(m)(-) (m=1-3), AlN(n)(-) (n=1-3, 5), Al(m)N(-) (n=2, 3), Al(2)N(n)(-) (n=2-4, 28, 30), N(n)(-) (n=2, 3), Al(4)N(7)(-) Al(8)N(n)(-) (n=1-6), and Al(13)N(n)(-) (n=9, 18, 20, 22, 24, 26, 28, 33, 35, 37, 39, 41 and 43) clusters were observed in negative ion mode. The formation of the stoichiometric Al(10) N(10) cluster was shown to be of low abundance. On the contrary, the laser ablation of nano-AlN led mainly to the formation of nitrogen-rich Al(m)N(n) clusters in both negative and positive ion mode. The stoichiometry of the Al(m)N(n) clusters was determined via isotopic envelope analysis and computer modelling. PMID:21598328

  2. Formation of aluminium, aluminium nitride and nitrogen clusters via laser ablation of nano aluminium nitride. Laser Desorption Ionisation and Matrix-Assisted Laser Desorption Ionisation Time-of-Flight Mass Spectrometry.

    PubMed

    Panyala, Nagender Reddy; Prysiazhnyi, Vadym; Slavíček, Pavel; Černák, Mirko; Havel, Josef

    2011-06-30

    Laser Desorption Ionisation (LDI) and Matrix-Assisted Laser Desorption Ionisation (MALDI) Time-of-Flight Mass Spectrometry (TOFMS) were used to study the pulsed laser ablation of aluminium nitride (AlN) nano powder. The formation of Al(m)(+) (m=1-3), N(n)(+) (n=4, 5), AlN(n)(+) (n=1-5, 19, 21), Al(m)N(+) (m=2-3), Al(3)N(2)(+), Al(9)N(n)(+) (n=5, 7, 9, 11 and 15), Al(11)N(n)(+) (n=4, 6, 10, 12, 19, 21, 23, and 25), and Al(13)N(n)(+) (n=25, 31, 32, 33, 34, 35, and 36) clusters was detected in positive ion mode. Similarly, Al(m)(-) (m=1-3), AlN(n)(-) (n=1-3, 5), Al(m)N(-) (n=2, 3), Al(2)N(n)(-) (n=2-4, 28, 30), N(n)(-) (n=2, 3), Al(4)N(7)(-) Al(8)N(n)(-) (n=1-6), and Al(13)N(n)(-) (n=9, 18, 20, 22, 24, 26, 28, 33, 35, 37, 39, 41 and 43) clusters were observed in negative ion mode. The formation of the stoichiometric Al(10) N(10) cluster was shown to be of low abundance. On the contrary, the laser ablation of nano-AlN led mainly to the formation of nitrogen-rich Al(m)N(n) clusters in both negative and positive ion mode. The stoichiometry of the Al(m)N(n) clusters was determined via isotopic envelope analysis and computer modelling.

  3. Assessment of Reproducibility of Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry for Bacterial and Yeast Identification

    PubMed Central

    Westblade, Lars F.; Garner, Omai B.; MacDonald, Karen; Bradford, Constance; Pincus, David H.; Mochon, A. Brian; Jennemann, Rebecca; Manji, Ryhana; Bythrow, Maureen; Lewinski, Michael A.; Burnham, Carey-Ann D.

    2015-01-01

    Matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry (MS) has revolutionized the identification of clinical bacterial and yeast isolates. However, data describing the reproducibility of MALDI-TOF MS for microbial identification are scarce. In this study, we show that MALDI-TOF MS-based microbial identification is highly reproducible and can tolerate numerous variables, including differences in testing environments, instruments, operators, reagent lots, and sample positioning patterns. Finally, we reveal that samples of bacterial and yeast isolates prepared for MALDI-TOF MS identification can be repeatedly analyzed without compromising organism identification. PMID:25926486

  4. Laser desorption/ionization time-of-flight mass spectrometry: A predictive tool for the lifetime of organic light emitting devices

    SciTech Connect

    Scholz, Sebastian; Meerheim, Rico; Luessem, Bjoern; Leo, Karl

    2009-01-26

    For improving the lifetime of organic light emitting devices (OLEDs), the analysis of the chemical degradation requires a deep understanding of the involved reaction pathways. We show that the dissociation reactions of phosphorescent emitters and the additional complexations with the used surrounding blocking layers are the dominant intrinsic degradation mechanisms in long living p-i-n type OLEDs. We use the laser desorption/ionization (LDI) time-of-flight mass spectrometry to correlate the laser-induced ion formation with the observed lifetime of the organic devices. The superlinear correlation between the LDI forced reactions and the lifetimes allows the prediction of the lifetime of an OLED with new materials.

  5. Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry-Based Method for Discrimination between Molecular Types of Cryptococcus neoformans and Cryptococcus gattii

    PubMed Central

    Posteraro, Brunella; Vella, Antonietta; Cogliati, Massimo; De Carolis, Elena; Florio, Ada Rita; Posteraro, Patrizia; Tortorano, Anna Maria

    2012-01-01

    We evaluated the usefulness of matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) for Cryptococcus identification at the species and subspecies levels by using an in-house database of 25 reference cryptococcal spectra. Eighty-one out of the 82 Cryptococcus isolates (72 Cryptococcus neoformans and 10 Cryptococcus gattii) tested were correctly identified with respect to their molecular type designations. We showed that MALDI-TOF MS is a practicable alternative to conventional mycology or DNA-based methods. PMID:22573595

  6. Rapid Identification of Positive Blood Cultures by Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry Using Prewarmed Agar Plates

    PubMed Central

    Bhatti, M. M.; Boonlayangoor, S.; Beavis, K. G.

    2014-01-01

    This study describes an inexpensive and straightforward method for identifying bacteria by matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) directly from positive blood cultures using prewarmed agar plates. Different inoculation methods and incubation times were evaluated to determine the optimal conditions. The two methods using pelleted material from positive culture bottles performed best. In particular, the pellet streak method correctly identified 94% of the Gram negatives following 4 h of incubation and 98% of the Gram positives following 6 h of incubation. PMID:25232166

  7. Rapid identification of positive blood cultures by matrix-assisted laser desorption ionization-time of flight mass spectrometry using prewarmed agar plates.

    PubMed

    Bhatti, M M; Boonlayangoor, S; Beavis, K G; Tesic, V

    2014-12-01

    This study describes an inexpensive and straightforward method for identifying bacteria by matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) directly from positive blood cultures using prewarmed agar plates. Different inoculation methods and incubation times were evaluated to determine the optimal conditions. The two methods using pelleted material from positive culture bottles performed best. In particular, the pellet streak method correctly identified 94% of the Gram negatives following 4 h of incubation and 98% of the Gram positives following 6 h of incubation.

  8. Advances in Identification of Clinical Yeast Isolates by Use of Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry

    PubMed Central

    Buchan, Blake W.

    2013-01-01

    Matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS)-based identification is being adopted by clinical laboratories for routine identification of microorganisms. To date, the majority of studies have focused on the performance and optimization of MALDI-TOF MS for the identification of bacterial isolates. We review recent literature describing the use of MALDI-TOF MS for the routine identification of a variety of yeasts and yeast-like isolates. Specific topics include the effect of optimized or streamlined extraction methods, modified scoring thresholds, expanded reference libraries, and the possibility of conducting antifungal susceptibility testing using MALDI-TOF MS. PMID:23426924

  9. Verification of a Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry Method for Diagnostic Identification of High-Consequence Bacterial Pathogens

    PubMed Central

    Tracz, Dobryan M.; Antonation, Kym S.

    2015-01-01

    We examined the utility of a single matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry method for the identification of security-sensitive biological agents (risk group 3 bacterial pathogens). The goal was 2-fold: to verify a method for inclusion into our scope of accreditation, and to assess the biological safety of extractions. We developed our sample flow to include a tube-based chemical extraction, followed by filtration, before processing on MALDI-TOF MS instruments in a containment level 2 laboratory. PMID:26677252

  10. Matrix-assisted and polymer-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of low molecular weight polystyrenes and polyethylene glycols.

    PubMed

    Woldegiorgis, Andreas; Löwenhielm, Peter; Björk, Anders; Roeraade, Johan

    2004-01-01

    Recently, matrices based on oligomers of dioxin and thiophene (polymer-assisted laser desorption/ionization (PALDI)) have been described for mass spectrometric (MS) analysis of low molecular weight compounds (Woldegiorgis A, von Kieseritzky F, Dahlstedt E, Hellberg J, Brinck T, Roeraade J. Rapid Commun. Mass Spectrom. 2004; 18: 841-852). In this paper, we report the use of PALDI matrices for low molecular weight polymers. An evaluation with polystyrene and polyethylene glycol showed that no charge transfer ionization occurs. Ionization is mediated through metal ion adduction. Comparison of matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) data for two very low molecular weight polymers with data obtained from size-exclusion chromatography (SEC) revealed a systematic difference regarding mean molecular weight and dispersity. Further, the mass spectra obtained with PALDI matrices had a higher signal-to-noise ratio than the spectra obtained with conventional matrices. For polymers with higher molecular weights (>1500 Da), the conventional matrices gave better performance. For evaluation of the MALDI spectra, three non-linear mathematical models were evaluated to model the cumulative distributions of the different oligomers and their maximal values of Mw, Mn and PDI. Models based on sigmoidal or Boltzmann equations proved to be most suitable. Objective modeling tools are necessary to compare different sample and instrumental conditions during method optimization of MALDI analysis of polymers, since the bias between MALDI and SEC data can be misleading.

  11. On-Tissue Derivatization via Electrospray Deposition for Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Imaging of Endogenous Fatty Acids in Rat Brain Tissues

    PubMed Central

    2016-01-01

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) is used for the multiplex detection and characterization of diverse analytes over a wide mass range directly from tissues. However, analyte coverage with MALDI MSI is typically limited to the more abundant compounds, which have m/z values that are distinct from MALDI matrix-related ions. On-tissue analyte derivatization addresses these issues by selectively tagging functional groups specific to a class of analytes, while simultaneously changing their molecular masses and improving their desorption and ionization efficiency. We evaluated electrospray deposition of liquid-phase derivatization agents as a means of on-tissue analyte derivatization using 2-picolylamine; we were able to detect a range of endogenous fatty acids with MALDI MSI. When compared with airbrush application, electrospray led to a 3-fold improvement in detection limits and decreased analyte delocalization. Six fatty acids were detected and visualized from rat cerebrum tissue using a MALDI MSI instrument operating in positive mode. MALDI MSI of the hippocampal area allowed targeted fatty acid analysis of the dentate gyrus granule cell layer and the CA1 pyramidal layer with a 20-μm pixel width, without degrading the localization of other lipids during liquid-phase analyte derivatization. PMID:27181709

  12. Detection of gaseous compounds by needle trap sampling and direct thermal-desorption photoionization mass spectrometry: concept and demonstrative application to breath gas analysis.

    PubMed

    Kleeblatt, Juliane; Schubert, Jochen K; Zimmermann, Ralf

    2015-02-01

    A fast detection method to analyze gaseous organic compounds in complex gas mixtures was developed, using a needle trap device (NTD) in conjunction with thermal-desorption photoionization time-of-flight mass spectrometry (TD-PI-TOFMS). The mass spectrometer was coupled via a deactivated fused silica capillary to an injector of a gas chromatograph. In the hot injector, the analytes collected on the NTD were thermally desorbed and directly transferred to the PI-TOFMS ion source. The molecules are softly ionized either by single photon ionization (SPI, 118 nm) or by resonance enhanced multiphoton ionization (REMPI, 266 nm), and the molecular ion signals are detected in the TOF mass analyzer. Analyte desorption and the subsequent PI-TOFMS detection step only lasts ten seconds. The specific selectivity of REMPI (i.e., aromatic compounds) and universal ionization characteristics render PI-MS as a promising detection system. As a first demonstrative application, the alveolar phase breath gas of healthy, nonsmoking subjects was sampled on NTDs. While smaller organic compounds such as acetone, acetaldehyde, isoprene, or cysteamine can be detected in the breath gas with SPI, REMPI depicts the aromatic substances phenol and indole at 266 nm. In the breath gas of a healthy, smoking male subject, several xenobiotic substances such as benzene, toluene, styrene, and ethylbenzene can be found as well. Furthermore, the NTD-REMPI-TOFMS setup was tested for breath gas taken from a mechanically ventilated pig under continuous intravenous propofol (2,6-diisopropylphenol, narcotic drug) infusion.

  13. On-Tissue Derivatization via Electrospray Deposition for Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Imaging of Endogenous Fatty Acids in Rat Brain Tissues.

    PubMed

    Wu, Qian; Comi, Troy J; Li, Bin; Rubakhin, Stanislav S; Sweedler, Jonathan V

    2016-06-01

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) is used for the multiplex detection and characterization of diverse analytes over a wide mass range directly from tissues. However, analyte coverage with MALDI MSI is typically limited to the more abundant compounds, which have m/z values that are distinct from MALDI matrix-related ions. On-tissue analyte derivatization addresses these issues by selectively tagging functional groups specific to a class of analytes, while simultaneously changing their molecular masses and improving their desorption and ionization efficiency. We evaluated electrospray deposition of liquid-phase derivatization agents as a means of on-tissue analyte derivatization using 2-picolylamine; we were able to detect a range of endogenous fatty acids with MALDI MSI. When compared with airbrush application, electrospray led to a 3-fold improvement in detection limits and decreased analyte delocalization. Six fatty acids were detected and visualized from rat cerebrum tissue using a MALDI MSI instrument operating in positive mode. MALDI MSI of the hippocampal area allowed targeted fatty acid analysis of the dentate gyrus granule cell layer and the CA1 pyramidal layer with a 20-μm pixel width, without degrading the localization of other lipids during liquid-phase analyte derivatization.

  14. Effect of delay time and grid voltage changes on the average molecular mass of polydisperse polymers and polymeric blends determined by delayed extraction matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Mineo, Placido; Vitalini, Daniele; Scamporrino, Emilio; Bazzano, Sebastiano; Alicata, Rossana

    2005-01-01

    The dependence of the calculated average molecular mass of a polyethylene glycol with a large polydispersity on the instrumental parameters adopted in the acquisition of mass spectra using delayed extraction matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (DE MALDI-TOFMS) was investigated. It has been shown that a combined effect of delay times and potential gradients can act on the ion cloud in the source chamber affecting both mass resolution and average molecular mass value of the analyzed polymeric sample. Also examined was a blend of two different polymers (a PEG and a PMMA commercial sample having a similar average molecular mass), which presents an additional problem concerning the discrimination among the different polymer species as a function of the experimental conditions. In this work, the best instrumental conditions to obtain both good resolution and a correct average molecular mass for the examined polydisperse sample are reported. PMID:16134231

  15. Signal enhancement in electrospray laser desorption/ionization mass spectrometry by using a black oxide-coated metal target and a relatively low laser fluence.

    PubMed

    Kononikhin, Alexey; Huang, Min-Zong; Popov, Igor; Kostyukevich, Yury; Kukaev, Evgeny; Boldyrev, Alexey; Spasskiy, Alexander; Leypunskiy, Ilya; Shiea, Jentaie; Nikolaev, Eugene

    2013-01-01

    The electrospray Laser desorption/ionization (ELDI) method is actively used for direct sample analysis and ambient mass spectrometry imaging. The optimizing of Laser desorption conditions is essential for this technology. In this work, we propose using a metal target with a black oxide (Fe3O4) coating to increase the signal in ELDI-MS for peptides and small proteins. The experiments were performed on an LTQ-FT mass spectrometer equipped with a home-made ELDI ion source. A cutter blade with black oxide coating was used as a target. A nitrogen laser was used with the following parameters: 337 nm, pulse duration 4ns, repetition rate 10 Hz, fluence to approximately 700 Jm(-2). More than a five times signal increase was observed for a substance P peptide when a coated and a non-coated metal target were compared. No ion signal was observed for proteins if the same fluence and the standard stainless steel target were used. With the assistance of the Fe3O4 coated metal target and a relatively low laser fluence < or =700 Jm(-2)), proteins such as insulin, ubiquitin and myoglobin were successfully ionized. It was demonstrated that the Fe3O4-coated metal target can be used efficiently to assist laser desorption and thus significantly increase the analyte signal in ELDI-MS. A relatively low laser fluence (< or = 700 Jm(-2)) was enough to desorb peptides and proteins (up to 17 kDal with the assistance of the Fe3O4-coated metal target under ambient conditions. PMID:24575623

  16. Fatal Nocardia farcinica Bacteremia Diagnosed by Matrix-Assisted Laser Desorption-Ionization Time of Flight Mass Spectrometry in a Patient with Myelodysplastic Syndrome Treated with Corticosteroids

    PubMed Central

    Moretti, Amedeo; Guercini, Francesco; Cardaccia, Angela; Furbetta, Leone; Agnelli, Giancarlo; Bistoni, Francesco; Mencacci, Antonella

    2013-01-01

    Nocardia farcinica is a Gram-positive weakly acid-fast filamentous saprophytic bacterium, an uncommon cause of human infections, acquired usually through the respiratory tract, often life-threatening, and associated with different clinical presentations. Predisposing conditions for N. farcinica infections include hematologic malignancies, treatment with corticosteroids, and any other condition of immunosuppression. Clinical and microbiological diagnoses of N. farcinica infections are troublesome, and the isolation and identification of the etiologic agent are difficult and time-consuming processes. We describe a case of fatal disseminated infection in a patient with myelodysplastic syndrome, treated with corticosteroids, in which N. farcinica has been isolated from blood culture and identified by Matrix-Assisted Laser Desorption-Ionization Time of Flight Mass Spectrometry. The patient died after 18 days of hospitalization in spite of triple antimicrobial therapy. Nocardia farcinica infection should be suspected in patients with history of malignancy, under corticosteroid therapy, suffering from subacute pulmonary infection,and who do not respond to conventional antimicrobial therapy. Matrix-Assisted Laser Desorption-Ionization Time of Flight Mass Spectrometry can be a valuable tool for rapid diagnosis of nocardiosis. PMID:23690786

  17. Matrix-assisted laser desorption ionization/mass spectrometry mapping of human immunodeficiency virus-gp120 epitopes recognized by a limited polyclonal antibody.

    PubMed

    Jeyarajah, S; Parker, C E; Summer, M T; Tomer, K B

    1998-02-01

    In this study we have applied epitope excision and epitope extraction strategies, combined with matrix assisted laser desorption/ionization mass spectrometry, to determine the fine structure of epitopes recognized by a polyclonal antibody to human immunodeficiency virus envelope glycoprotein gp120. This is the first application of this approach to epitope mapping on a large, heavily glycosylated protein. In the epitope excision method, gp120 in the native form is first bound to the antibody immobilized on sepharose beads and cleaved with endoproteinase enzymes. In the epitope extraction method, the gp120 was first proteolytically cleaved and then allowed to react with the immobilized antibody. The fragments that remain bound to the antibody, after repeated washing to remove the unbound peptides, contain the antigenic region that is recognized by the antibody, and the bound peptides in both methods can be characterized by direct analysis of the immobilized antibody by matrix assisted laser desorption ionization/mass spectrometry. In this study we have carried out epitope excision and extraction experiments with three different enzymes and have identified residues 472-478 as a major epitope. In addition, antigenic regions containing minor epitopes have also been identified.

  18. Matrix-free and material-enhanced laser desorption/ionization mass spectrometry for the analysis of low molecular weight compounds.

    PubMed

    Rainer, Matthias; Qureshi, Muhammad Nasimullah; Bonn, Günther Karl

    2011-06-01

    The application of matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) for the analysis of low molecular weight (LMW) compounds, such as pharmacologically active constituents or metabolites, is usually hampered by employing conventional MALDI matrices owing to interferences caused by matrix molecules below 700 Da. As a consequence, interpretation of mass spectra remains challenging, although matrix suppression can be achieved under certain conditions. Unlike the conventional MALDI methods which usually suffer from background signals, matrix-free techniques have become more and more popular for the analysis of LMW compounds. In this review we describe recently introduced materials for laser desorption/ionization (LDI) as alternatives to conventionally applied MALDI matrices. In particular, we want to highlight a new method for LDI which is referred to as matrix-free material-enhanced LDI (MELDI). In matrix-free MELDI it could be clearly shown, that besides chemical functionalities, the material's morphology plays a crucial role regarding energy-transfer capabilities. Therefore, it is of great interest to also investigate parameters such as particle size and porosity to study their impact on the LDI process. Especially nanomaterials such as diamond-like carbon, C(60) fullerenes and nanoparticulate silica beads were found to be excellent energy-absorbing materials in matrix-free MELDI.

  19. A method for measuring vapor pressures of low-volatility organic aerosol compounds using a thermal desorption particle beam mass spectrometer.

    PubMed

    Chattopadhyay, S; Tobias, H J; Ziemann, P J

    2001-08-15

    A temperature-programmed thermal desorption method for measuring vapor pressures of low-volatility organic aerosol compounds has been developed. The technique employs a thermal desorption particle beam mass spectrometer we have recently developed for real-time composition analysis of organic aerosols. Particles are size selected using a differential mobility analyzer, sampled into a high-vacuum chamber as an aerodynamically focused beam, collected by impaction on a cryogenically cooled surface, slowly vaporized by resistive heating, and analyzed in a quadrupole mass spectrometer. A simple evaporation model developed from the kinetic theory of gases is used to calculate compound vapor pressures over the temperature range of evaporation. The data are fit to a Clausius-Clapeyron equation to obtain a relationship between vapor pressure and temperature and to determine the heat of vaporization. The technique has been evaluated using C13-C18 monocarboxylic and C6-C8 dicarboxylic acids, which have vapor pressures at 25 degrees C of approximately 10(-4) - 10(-6) Pa, but less volatile compounds can also be analyzed. The method is relatively simple and rapid and yields vapor pressures and heats of vaporization that are in good agreement with literature values. The technique will be used to generate a new database of vapor pressures for low-volatility atmospheric organic compounds.

  20. Development of Spectral Pattern Matching Approaches to Matrix-assisted Laser Desorption/Ionization Time-of-flight Mass Spectrometry for Bacterial Identification

    SciTech Connect

    Jarman, Kristin H.; Wahl, Karen L.

    2005-12-01

    The concept of rapid microorganism identification using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) dates back to the mid-1990’s. Prior to 1998, researchers relied on visual inspection in an effort to demonstrate feasibility of MALDI-MS for bacterial identification (Holland, Wilkes et al. 1996), (Krishnamurthy and Ross 1996), (Claydon, Davey et al. 1996). In general, researchers in these early studies visually compared the biomarker intensity profiles between different organisms and between replicates of the same organism to show that MALDI signatures are unique and reproducible. Manual tabulation and comparison of potential biomarker mass values observed for different organisms was used by numerous researchers to qualitatively characterize microorganisms using MALDI-MS spectra (e.g. (Lynn, Chung et al. 1999), (Winkler, Uher et al. 1999), (Ryzhov, Hathout et al. 2000), (Nilsson 1999)).

  1. Determination of trichloroanisole and trichlorophenol in wineries' ambient air by passive sampling and thermal desorption-gas chromatography coupled to tandem mass spectrometry.

    PubMed

    Camino-Sánchez, F J; Bermúdez-Peinado, R; Zafra-Gómez, A; Ruíz-García, J; Vílchez-Quero, J L

    2015-02-01

    The present paper describes the calibration of selected passive samplers used in the quantitation of trichlorophenol and trichloroanisole in wineries' ambient air, by calculating the corresponding sampling rates. The method is based on passive sampling with sorbent tubes and involves thermal desorption-gas chromatography-triple quadrupole mass spectrometry analysis. Three commercially available sorbents were tested using sampling cartridges with a radial design instead of axial ones. The best results were found for Tenax TA™. Sampling rates (R-values) for the selected sorbents were determined. Passive sampling was also used for accurately determining the amount of compounds present in the air. Adequate correlation coefficients between the mass of the target analytes and exposure time were obtained. The proposed validated method is a useful tool for the early detection of trichloroanisole and its precursor trichlorophenol in wineries' ambient air while avoiding contamination of wine or winery facilities.

  2. Inkjet-printed gold nanoparticle surfaces for the detection of low molecular weight biomolecules by laser desorption/ionization mass spectrometry.

    PubMed

    Marsico, Alyssa L M; Creran, Brian; Duncan, Bradley; Elci, S Gokhan; Jiang, Ying; Onasch, Timothy B; Wormhoudt, Joda; Rotello, Vincent M; Vachet, Richard W

    2015-11-01

    Effective detection of low molecular weight compounds in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is often hindered by matrix interferences in the low m/z region of the mass spectrum. Here, we show that monolayer-protected gold nanoparticles (AuNPs) can serve as alternate matrices for the very sensitive detection of low molecular weight compounds such as amino acids. Amino acids can be detected at low fmol levels with minimal interferences by properly choosing the AuNP deposition method, density, size, and monolayer surface chemistry. By inkjet-printing AuNPs at various densities, we find that AuNP clusters are essential for obtaining the greatest sensitivity. Graphical Abstract ᅟ.

  3. System and method of infrared matrix-assisted laser desorption/ionization mass spectrometry in polyacrylamide gels

    DOEpatents

    Haglund, Jr., Richard F.; Ermer, David R.; Baltz-Knorr, Michelle Lee

    2004-11-30

    A system and method for desorption and ionization of analytes in an ablation medium. In one embodiment, the method includes the steps of preparing a sample having analytes in a medium including at least one component, freezing the sample at a sufficiently low temperature so that at least part of the sample has a phase transition, and irradiating the frozen sample with short-pulse radiation to cause medium ablation and desorption and ionization of the analytes. The method further includes the steps of selecting a resonant vibrational mode of at least one component of the medium and selecting an energy source tuned to emit radiation substantially at the wavelength of the selected resonant vibrational mode. The medium is an electrophoresis medium having polyacrylamide. In one embodiment, the energy source is a laser, where the laser can be a free electron laser tunable to generate short-pulse radiation. Alternatively, the laser can be a solid state laser tunable to generate short-pulse radiation. The laser can emit light at various ranges of wavelength.

  4. Direct matrix-assisted laser desorption ionization time-of-flight mass spectrometric analysis of lysozyme contained in hen egg white.

    PubMed

    Smolira, Anna; Hałas, Stanisław

    2016-01-01

    As a natural antibacterial peptide, lysozyme (LZ) is widely used in medicine and the food industry. Despite many years of research on this compound, its new antibacterial properties are still to be determined. The primary aim of this work is to demonstrate the application of the matrix-assisted laser desorption ionization (MALDI) time-of-flight mass spectrometric analysis of LZ directly in hen egg white samples without extraction thereof. The egg white samples were kept over 10 weeks at room temperature and measured every week. The resulting positive and negative ion mass spectra were then compared to determine the intensity of the LZ mass peak. Storage of the egg white for over 10 weeks did not influence the LZ mass peak intensity (both positive and negative). It can be concluded that the LZ concentration in the egg white samples did not vary with time. The effect of the matrix/sample ratio on LZ detection was also examined, and it was found to be different in the case of positive and negative ionization. The mass peaks of LZ oligomeric forms were observed in all mass spectra, so the MALDI method could be used in subsequent studies. PMID:26863071

  5. Advanced stored waveform inverse Fourier transform technique for a matrix-assisted laser desorption/ionization quadrupole ion trap mass spectrometer.

    PubMed

    Doroshenko, V M; Cotter, R J

    1996-01-01

    The stored waveform inverse Fourier transform (SWIFT) technique is used for broadband excitation of ions in an ion-trap mass spectrometer to perform mass-selective accumulation, isolation, and fragmentation of peptide ions formed by matrix-assisted laser desorption/ionization. Unit mass resolution is achieved for isolation of ions in the range of m/z up to 1300 using a two-step isolation technique with stretched-in-time narrow band SWIFT pulses at the second stage. The effect of 'stretched-in-time' waveforms is similar to that observed previously for mass-scan-rate reduction. The asymmetry phenomenon resulting from the stretched ion-trap electrode geometry is observed during application of normal and time-reversed waveforms and is similar to the asymmetry effects observed for forward and reverse mass scans in the resonance ejection mode. Mass-selective accumulation of ions from multiple laser shots was accomplished using a method described earlier that involves increasing the trapping voltage during ion introduction for more efficient trapping of ions.

  6. Intact lipid imaging of mouse brain samples: MALDI, nanoparticle-laser desorption ionization, and 40 keV argon cluster secondary ion mass spectrometry.

    PubMed

    Mohammadi, Amir Saeid; Phan, Nhu T N; Fletcher, John S; Ewing, Andrew G

    2016-09-01

    We have investigated the capability of nanoparticle-assisted laser desorption ionization mass spectrometry (NP-LDI MS), matrix-assisted laser desorption ionization (MALDI) MS, and gas cluster ion beam secondary ion mass spectrometry (GCIB SIMS) to provide maximum information available in lipid analysis and imaging of mouse brain tissue. The use of Au nanoparticles deposited as a matrix for NP-LDI MS is compared to MALDI and SIMS analysis of mouse brain tissue and allows selective detection and imaging of groups of lipid molecular ion species localizing in the white matter differently from those observed using conventional MALDI with improved imaging potential. We demonstrate that high-energy (40 keV) GCIB SIMS can act as a semi-soft ionization method to extend the useful mass range of SIMS imaging to analyze and image intact lipids in biological samples, closing the gap between conventional SIMS and MALDI techniques. The GCIB SIMS allowed the detection of more intact lipid compounds in the mouse brain compared to MALDI with regular organic matrices. The 40 keV GCIB SIMS also produced peaks observed in the NP-LDI analysis, and these peaks were strongly enhanced in intensity by exposure of the sample to trifluororacetic acid (TFA) vapor prior to analysis. These MS techniques for imaging of different types of lipids create a potential overlap and cross point that can enhance the information for imaging lipids in biological tissue sections. Graphical abstract Schematic of mass spectral imaging of a mouse brain tissue using GCIB-SIMS and MALDI techniques. PMID:27549796

  7. Intact lipid imaging of mouse brain samples: MALDI, nanoparticle-laser desorption ionization, and 40 keV argon cluster secondary ion mass spectrometry.

    PubMed

    Mohammadi, Amir Saeid; Phan, Nhu T N; Fletcher, John S; Ewing, Andrew G

    2016-09-01

    We have investigated the capability of nanoparticle-assisted laser desorption ionization mass spectrometry (NP-LDI MS), matrix-assisted laser desorption ionization (MALDI) MS, and gas cluster ion beam secondary ion mass spectrometry (GCIB SIMS) to provide maximum information available in lipid analysis and imaging of mouse brain tissue. The use of Au nanoparticles deposited as a matrix for NP-LDI MS is compared to MALDI and SIMS analysis of mouse brain tissue and allows selective detection and imaging of groups of lipid molecular ion species localizing in the white matter differently from those observed using conventional MALDI with improved imaging potential. We demonstrate that high-energy (40 keV) GCIB SIMS can act as a semi-soft ionization method to extend the useful mass range of SIMS imaging to analyze and image intact lipids in biological samples, closing the gap between conventional SIMS and MALDI techniques. The GCIB SIMS allowed the detection of more intact lipid compounds in the mouse brain compared to MALDI with regular organic matrices. The 40 keV GCIB SIMS also produced peaks observed in the NP-LDI analysis, and these peaks were strongly enhanced in intensity by exposure of the sample to trifluororacetic acid (TFA) vapor prior to analysis. These MS techniques for imaging of different types of lipids create a potential overlap and cross point that can enhance the information for imaging lipids in biological tissue sections. Graphical abstract Schematic of mass spectral imaging of a mouse brain tissue using GCIB-SIMS and MALDI techniques.

  8. Solid phase synthesis of somatostatin-28 II. A new biologically active octacosapeptide from anglerfish pancreatic islets.

    PubMed

    Nicolas, P; Delfour, A; Boussetta, H; Morel, A; Rholam, M; Cohen, P

    1986-10-30

    Somatostatin-28 II, an octacosapeptide recently isolated from anglerfish pancreatic islets, was synthetized by the solid phase method along with its somatostatin-14 II and somatostatin-28 II-(1-12) corresponding domains. Homogeneity of the synthetic peptides was demonstrated by analytical RP-HPLC, thin layer chromatography and electrophoresis. The peptides were further characterized by amino acids analysis, fast atomic bombarding mass spectrometry and/or 252Cf plasma desorption mass spectrometry. Synthetic somatostatin-28 II and somatostatin-14 II displace equally well the potent agonist (Tyr0,D-Trp8)-somatostatin-14 from its specific binding sites on anterior pituitary cells membranes. Both peptides activate adenylate cyclase from dispersed rat anterior pituitary cells. PMID:2877662

  9. Analysis of Antiretrovirals in Single Hair Strands for Evaluation of Drug Adherence with Infrared-Matrix-Assisted Laser Desorption Electrospray Ionization Mass Spectrometry Imaging.

    PubMed

    Rosen, Elias P; Thompson, Corbin G; Bokhart, Mark T; Prince, Heather M A; Sykes, Craig; Muddiman, David C; Kashuba, Angela D M

    2016-01-19

    Adherence to a drug regimen can be a strong predictor of health outcomes, and validated measures of adherence are necessary at all stages of therapy from drug development to prescription. Many of the existing metrics of drug adherence (e.g., self-report, pill counts, blood monitoring) have limitations, and analysis of hair strands has recently emerged as an objective alternative. Traditional methods of hair analysis based on LC-MS/MS (segmenting strands at ≥1 cm length) are not capable of preserving a temporal record of drug intake at higher resolution than approximately 1 month. Here, we evaluated the detectability of HIV antiretrovirals (ARVs) in hair from a range of drug classes using infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) mass spectrometry imaging (MSI) with 100 μm resolution. Infrared laser desorption of hair strands was shown to penetrate into the strand cortex, allowing direct measurement by MSI without analyte extraction. Using optimized desorption conditions, a linear correlation between IR-MALDESI ion abundance and LC-MS/MS response was observed for six common ARVs with estimated limits of detection less than or equal to 1.6 ng/mg hair. The distribution of efavirenz (EFV) was then monitored in a series of hair strands collected from HIV infected, virologically suppressed patients. Because of the role hair melanin plays in accumulation of basic drugs (like most ARVs), an MSI method to quantify the melanin biomarker pyrrole-2,3,5-tricarboxylic acid (PTCA) was evaluated as a means of normalizing drug response between patients to develop broadly applicable adherence criteria. PMID:26688545

  10. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for the identification of environmental organisms: the Planctomycetes paradigm.

    PubMed

    Cayrou, Caroline; Raoult, Didier; Drancourt, Michel

    2010-12-01

    We have developed a matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS)-based identification technique for Planctomycetes organisms, which are used here as bacteria of suitable diversity at genus and species level for testing resolution of the method. Planctomyces maris ATCC 29201, Planctomyces brasiliensis ATCC 49424(T) , P. brasiliensis ATCC 49425, Planctomyces limnophilus ATCC 43296(T) , Blastopirellula marina ATCC 49069(T) , Rhodopirellula baltica DSM 10527(T) and Gemmata obscuriglobus DSM 5831(T) were cultured on half-strength marine broth and agar, or alternatively on caulobacter broth and agar. The resulting pellets of organisms (liquid) or colonies (solid agar) were directly applied to a MALDI-TOF plate. This yielded a reproducible, unique protein profiles comprising 23-39 peaks ranging in size from 2403 to 12 091 Da. These peaks were unambiguously distinguished from any of the 3038 bacterial spectra in the Brüker database. Matrix-assisted laser desorption/ionization time-of-flight patterns were similar for isolates grown in solid and in liquid medium, albeit the patterns from solid growth were more easily interpretable. After the incorporation of the herein determined profiles into the Brüker database, Planctomycetes isolates were blindly identified within 10 min, with an identification score in the range of 1.8 to 2.3. Matrix-assisted laser desorption/ionization time-of-flight-based clustering of these Planctomycetes organisms was consistent with 16S rDNA-based phylogeny. However, the incorporation of additional non-Planctomycetes MALDI-TOF profiles in the analysis resulted in inconsequential clustering. In conclusion, MALDI-TOF protein profiling is a new approach for the rapid and accurate identification of cultured environmental organisms, as illustrated in this study through the analysis of Planctomycetes. PMID:23766281

  11. Analysis of Antiretrovirals in Single Hair Strands for Evaluation of Drug Adherence with Infrared-Matrix-Assisted Laser Desorption Electrospray Ionization Mass Spectrometry Imaging.

    PubMed

    Rosen, Elias P; Thompson, Corbin G; Bokhart, Mark T; Prince, Heather M A; Sykes, Craig; Muddiman, David C; Kashuba, Angela D M

    2016-01-19

    Adherence to a drug regimen can be a strong predictor of health outcomes, and validated measures of adherence are necessary at all stages of therapy from drug development to prescription. Many of the existing metrics of drug adherence (e.g., self-report, pill counts, blood monitoring) have limitations, and analysis of hair strands has recently emerged as an objective alternative. Traditional methods of hair analysis based on LC-MS/MS (segmenting strands at ≥1 cm length) are not capable of preserving a temporal record of drug intake at higher resolution than approximately 1 month. Here, we evaluated the detectability of HIV antiretrovirals (ARVs) in hair from a range of drug classes using infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) mass spectrometry imaging (MSI) with 100 μm resolution. Infrared laser desorption of hair strands was shown to penetrate into the strand cortex, allowing direct measurement by MSI without analyte extraction. Using optimized desorption conditions, a linear correlation between IR-MALDESI ion abundance and LC-MS/MS response was observed for six common ARVs with estimated limits of detection less than or equal to 1.6 ng/mg hair. The distribution of efavirenz (EFV) was then monitored in a series of hair strands collected from HIV infected, virologically suppressed patients. Because of the role hair melanin plays in accumulation of basic drugs (like most ARVs), an MSI method to quantify the melanin biomarker pyrrole-2,3,5-tricarboxylic acid (PTCA) was evaluated as a means of normalizing drug response between patients to develop broadly applicable adherence criteria.

  12. Natural products in Glycyrrhiza glabra (licorice) rhizome imaged at the cellular level by atmospheric pressure matrix-assisted laser desorption/ionization tandem mass spectrometry imaging.

    PubMed

    Li, Bin; Bhandari, Dhaka Ram; Janfelt, Christian; Römpp, Andreas; Spengler, Bernhard

    2014-10-01

    The rhizome of Glycyrrhiza glabra (licorice) was analyzed by high-resolution mass spectrometry imaging and tandem mass spectrometry imaging. An atmospheric pressure matrix-assisted laser desorption/ionization imaging ion source was combined with an orbital trapping mass spectrometer in order to obtain high-resolution imaging in mass and space. Sections of the rhizome were imaged with a spatial resolution of 10 μm in the positive ion mode, and a large number of secondary metabolites were localized and identified based on their accurate mass and MS/MS fragmentation patterns. Major tissue-specific metabolites, including free flavonoids, flavonoid glycosides and saponins, were successfully detected and visualized in images, showing their distributions at the cellular level. The analytical power of the technique was tested in the imaging of two isobaric licorice saponins with a mass difference of only 0.02 Da. With a mass resolving power of 140 000 and a bin width of 5 ppm in the image processing, the two compounds were well resolved in full-scan mode, and appeared with different distributions in the tissue sections. The identities of the compounds and their distributions were validated in a subsequent MS/MS imaging experiment, thereby confirming their identities and excluding possible analyte interference. The use of high spatial resolution, high mass resolution and tandem mass spectrometry in imaging experiments provides significant information about the biosynthetic pathway of flavonoids and saponins in legume species, combing the spatially resolved chemical information with morphological details at the microscopic level. Furthermore, the technique offers a scheme capable of high-throughput profiling of metabolites in plant tissues.

  13. Sensitive indoor air monitoring of monoterpenes using different adsorbents and thermal desorption gas chromatography with mass-selective detection.

    PubMed

    Hollender, Juliane; Sandner, Frank; Möller, Manfred; Dott, Wolfgang

    2002-07-12

    A simple method using active trapping on adsorbents and thermal desorption followed by GC-MS analysis was developed for the indoor air monitoring of monoterpenes. The study was carried out using a dynamically generated atmosphere consisting of 11 monoterpenes: camphene, camphor, delta 3-carene, 1,8-cineol, limonene, linalool, alpha-pinene, beta-pinene, alpha-terpinene, gamma-terpinene, fenchyl alcohol. The influence of the different adsorbents Tenax TA, Tenax GR, Carbosieve SIII, Chromosorb 106 on the yield of six selected monoterpenes at indoor air concentrations was studied. The adsorbent Tenax GR gave relatively the best yields followed by Tenax TA. Detection limits of approximately 1 microgram m3 were determined with Tenax GR for most of the monoterpenes.

  14. Determination of polyethylene glycol end group functionalities by combination of selective reactions and characterization by matrix assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Zhang, Boyu; Zhang, Hong; Myers, Brittany K; Elupula, Ravinder; Jayawickramarajah, Janarthanan; Grayson, Scott M

    2014-03-13

    End groups play a critical role in macromolecular coupling reactions for building complex polymer architectures, yet their identity and purity can be difficult to ascertain using traditional analytical technique. Recent advances in mass spectrometry techniques have made matrix-assisted laser desorption/ionization time-of-fight (MALDI-TOF) mass spectrometry a rapid and powerful tool for providing detailed information about the identity and purity of homopolymer end groups. In this work, MALDI-TOF mass spectrometry was used to study end groups of linear polyethylene glycols. In particular, the identifications of alcohol, amine and thiol end groups are investigated because these nucleophilic moieties are among the most common within biological and synthetic macromolecules. Through comparative characterization of alcohol, amine, and thiol end groups, the exact identification of these end groups could be confirmed by selective and quantitative modification. The precision of this technique enables the unambiguous differentiation of primary amino groups relative to hydroxyl groups, which differ by only 1 mass unit. In addition, the quantitative conversion of various polyethylene glycol end groups using highly efficient coupling reactions such as the thiol-ene and azide-alkyne click reactions can be confirmed using MALDI-TOF mass spectrometry.

  15. Application of an automatic thermal desorption-gas chromatography-mass spectrometry system for the analysis of polycyclic aromatic hydrocarbons in airborne particulate matter.

    PubMed

    Gil-Moltó, J; Varea, M; Galindo, N; Crespo, J

    2009-02-27

    The application of the thermal desorption (TD) method coupled with gas chromatography-mass spectrometry (GC-MS) to the analysis of aerosol organics has been the focus of many studies in recent years. This technique overcomes the main drawbacks of the solvent extraction approach such as the use of large amounts of toxic organic solvents and long and laborious extraction processes. In this work, the application of an automatic TD-GC-MS instrument for the determination of particle-bound polycyclic aromatic hydrocarbons (PAHs) is evaluated. This device offers the advantage of allowing the analysis of either gaseous or particulate organics without any modification. Once the thermal desorption conditions for PAH extraction were optimised, the method was verified on NIST standard reference material (SRM) 1649a urban dust, showing good linearity, reproducibility and accuracy for all target PAHs. The method has been applied to PM10 and PM2.5 samples collected on quartz fibre filters with low volume samplers, demonstrating its capability to quantify PAHs when only a small amount of sample is available. PMID:19150718

  16. Exploring Biosignatures Associated with Thenardite by Geomatrix-Assisted Laser Desorption/Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (GALDI-FTICR-MS)

    SciTech Connect

    C. Doc Richardson; Nancy W. Hinman; Timothy R. McJunkin; J. Michelle Kotler; Jill R. Scott

    2008-10-01

    Geomatrix-assisted laser desorption/ionization (GALDI) in conjunction with a Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS) has been employed to determine how effectively bio/organic molecules associated with the mineral thenardite (Na2SO4) can be detected. GALDI is based on the ability of the mineral host to assist desorption and ionization of bio/organic molecules without additional sample preparation. When glycine was mixed with thenardite, glycine was deprotonated to produce C2H4NO-2 at m/z 74.025. The combination of stearic acid with thenardite produced a complex cluster ion at m/z 390.258 in the negative mode, which was assigned a composition ofC18H39O7Na-. Anatural sample of thenardite from Searles Lake in California also produced a peak at m/z 390.260. The bio/organic signatures in both the laboratory-based and natural samples were heterogeneously dispersed as revealed by chemical imaging. The detection limits for the stearic acid and thenardite combination were estimated to be 3 parts per trillion or~7 zeptomoles (10-21) per laser spot. Attempts to improve the signal-to-noise ratio by co-adding FTICR-MS data predetermined to contain the biosignatures of interest revealed problems due to a lack of phase coherence between data sets.

  17. Optimization of a Dynamic Headspace-Thermal Desorption-Gas Chromatography/Mass Spectrometry procedure for the determination of furfurals in vinegars.

    PubMed

    Manzini, Simona; Durante, Caterina; Baschieri, Carlo; Cocchi, Marina; Sighinolfi, Simona; Totaro, Sara; Marchetti, Andrea

    2011-08-15

    The use of a Dynamic Headspace System (DHS) device combined with a Thermal Desorption Unit (TDU) interfaced to a Gas Chromatography/Mass Spectrometry (GC/MS) system is proposed for the determination of furfurals in oenological products. An experimental design protocol has been employed for the optimization of the instrumental settings concerning DHS and TDU extraction and desorption steps. It has been possible to individuate the following optimized conditions: incubation temperature 40°C, purge volume 800 mL, dry volume 1500 mL, TDU hold time 5 min and incubation time 10 min. The performance of two different SPE sorbents, namely Tenax TA and Tenax GR used for the furfurals trapping, was investigated too. The developed DHS sampling procedure showed good reproducibility values with a RSD% lower than 10% for all the monitored species. The optimized experimental settings have been used to determine furfurals in several vinegar samples obtained by traditional procedure starting from cooked grape musts, i.e. in Aceto Balsamico Tradizionale di Modena (ABTM). In fact, the control of these species is extremely important for quality and safety issues.

  18. Direct Imaging Mass Spectrometry of Plant Leaves Using Surface-assisted Laser Desorption/Ionization with Sputter-deposited Platinum Film.

    PubMed

    Ozawa, Tomoyuki; Osaka, Issey; Hamada, Satoshi; Murakami, Tatsuya; Miyazato, Akio; Kawasaki, Hideya; Arakawa, Ryuichi

    2016-01-01

    Plant leaves administered with systemic insecticides as agricultural chemicals were analyzed using imaging mass spectrometry (IMS). Matrix-assisted laser desorption/ionization (MALDI) is inadequate for the detection of insecticides on leaves because of the charge-up effect that occurs on the non-conductive surface of the leaves. In this study, surface-assisted laser desorption/ionization with a sputter-deposited platinum film (Pt-SALDI) was used for direct analysis of chemicals in plant leaves. Sputter-deposited platinum (Pt) films were prepared on leaves administered with the insecticides. A sputter-deposited Pt film with porous structure was used as the matrix for Pt-SALDI. Acephate and acetamiprid contained in the insecticides on the leaves could be detected using Pt-SALDI-MS, but these chemical components could not be adequately detected using MALDI-MS because of the charge-up effect. Enhancement of ion yields for the insecticides was achieved using Pt-SALDI, accompanied by prevention of the charge-up effect by the conductive Pt film. The movement of systemic insecticides in plants could be observed clearly using Pt-SALDI-IMS. The distribution and movement of components of systemic insecticides on leaves could be analyzed directly using Pt-SALDI-IMS. Additionally, changes in the properties of the chemicals with time, as an indicator of the permeability of the insecticides, could be evaluated. PMID:27169661

  19. Model verification of thermal programmed desorption-mass spectrometry for estimation of release energy values for polycyclic aromatic hydrocarbons on mineral sorbents.

    PubMed

    Nicholl, Sara I; Talley, Jeffrey W; Silliman, Stephan

    2004-11-01

    The physical availability of organic compounds in soil and sediment strongly influences their bioavailability and toxicity. Previous work has indicated that physical availability changes throughout the processes of aging and treatment and that it can be linked to the energy required to release the compound from its sorbent matrix, with a higher energy indicating a more tightly bound compound. This study focused on determining release energy values for various mineral geosorbents (glass beads, sand, and kaolin) contaminated with a 16 polycyclic aromatic hydrocarbon (PAH) mixture. The sorbents were analyzed using thermal program desorption/mass spectrometry (TPD/MS) and the release energy values were calculated from the resulting thermograms utilizing a nonlinear fit of the analytical solution to a simplified version of the Polanyi-Wigner equation. This solution method resulted in a series of combinations of values for the pre-exponential factor (v) and release energy (E) that produced desorption rate curves with similar errors when fit to actual data sets. These combinations can be viewed as an error surface, which clearly shows a valley of minimum error values spanning the range of both E and v. This indicates that this method may not provide a unique set of E- and v-values and suggests that the simplified version of the Polanyi-Wigner equation cannot be used to determine release energy based on TPD data alone.

  20. Application of an automatic thermal desorption-gas chromatography-mass spectrometry system for the analysis of polycyclic aromatic hydrocarbons in airborne particulate matter.

    PubMed

    Gil-Moltó, J; Varea, M; Galindo, N; Crespo, J

    2009-02-27

    The application of the thermal desorption (TD) method coupled with gas chromatography-mass spectrometry (GC-MS) to the analysis of aerosol organics has been the focus of many studies in recent years. This technique overcomes the main drawbacks of the solvent extraction approach such as the use of large amounts of toxic organic solvents and long and laborious extraction processes. In this work, the application of an automatic TD-GC-MS instrument for the determination of particle-bound polycyclic aromatic hydrocarbons (PAHs) is evaluated. This device offers the advantage of allowing the analysis of either gaseous or particulate organics without any modification. Once the thermal desorption conditions for PAH extraction were optimised, the method was verified on NIST standard reference material (SRM) 1649a urban dust, showing good linearity, reproducibility and accuracy for all target PAHs. The method has been applied to PM10 and PM2.5 samples collected on quartz fibre filters with low volume samplers, demonstrating its capability to quantify PAHs when only a small amount of sample is available.

  1. Direct Imaging Mass Spectrometry of Plant Leaves Using Surface-assisted Laser Desorption/Ionization with Sputter-deposited Platinum Film.

    PubMed

    Ozawa, Tomoyuki; Osaka, Issey; Hamada, Satoshi; Murakami, Tatsuya; Miyazato, Akio; Kawasaki, Hideya; Arakawa, Ryuichi

    2016-01-01

    Plant leaves administered with systemic insecticides as agricultural chemicals were analyzed using imaging mass spectrometry (IMS). Matrix-assisted laser desorption/ionization (MALDI) is inadequate for the detection of insecticides on leaves because of the charge-up effect that occurs on the non-conductive surface of the leaves. In this study, surface-assisted laser desorption/ionization with a sputter-deposited platinum film (Pt-SALDI) was used for direct analysis of chemicals in plant leaves. Sputter-deposited platinum (Pt) films were prepared on leaves administered with the insecticides. A sputter-deposited Pt film with porous structure was used as the matrix for Pt-SALDI. Acephate and acetamiprid contained in the insecticides on the leaves could be detected using Pt-SALDI-MS, but these chemical components could not be adequately detected using MALDI-MS because of the charge-up effect. Enhancement of ion yields for the insecticides was achieved using Pt-SALDI, accompanied by prevention of the charge-up effect by the conductive Pt film. The movement of systemic insecticides in plants could be observed clearly using Pt-SALDI-IMS. The distribution and movement of components of systemic insecticides on leaves could be analyzed directly using Pt-SALDI-IMS. Additionally, changes in the properties of the chemicals with time, as an indicator of the permeability of the insecticides, could be evaluated.

  2. Model verification of thermal programmed desorption-mass spectrometry for estimation of release energy values for polycyclic aromatic hydrocarbons on mineral sorbents.

    PubMed

    Nicholl, Sara I; Talley, Jeffrey W; Silliman, Stephan

    2004-11-01

    The physical availability of organic compounds in soil and sediment strongly influences their bioavailability and toxicity. Previous work has indicated that physical availability changes throughout the processes of aging and treatment and that it can be linked to the energy required to release the compound from its sorbent matrix, with a higher energy indicating a more tightly bound compound. This study focused on determining release energy values for various mineral geosorbents (glass beads, sand, and kaolin) contaminated with a 16 polycyclic aromatic hydrocarbon (PAH) mixture. The sorbents were analyzed using thermal program desorption/mass spectrometry (TPD/MS) and the release energy values were calculated from the resulting thermograms utilizing a nonlinear fit of the analytical solution to a simplified version of the Polanyi-Wigner equation. This solution method resulted in a series of combinations of values for the pre-exponential factor (v) and release energy (E) that produced desorption rate curves with similar errors when fit to actual data sets. These combinations can be viewed as an error surface, which clearly shows a valley of minimum error values spanning the range of both E and v. This indicates that this method may not provide a unique set of E- and v-values and suggests that the simplified version of the Polanyi-Wigner equation cannot be used to determine release energy based on TPD data alone. PMID:15559267

  3. Analysis of semi-volatile organic compounds in indoor suspended particulate matter by thermal desorption coupled with gas chromatography/mass spectrometry.

    PubMed

    Mercier, Fabien; Glorennec, Philippe; Blanchard, Olivier; Le Bot, Barbara

    2012-09-01

    People are exposed to multiple pollutants, especially indoors. In the perspective of a cumulative risk assessment, a multi-residue analytical method was developed to assess the contamination of indoor suspended particulate matter by 55 semi-volatile organic compounds (SVOCs) including musk fragrances, organochlorines (OCs), organophosphates (OPs), polycyclic aromatic hydrocarbons (PAHs), polybromodiphenylethers (PBDEs), polychlorobiphenyls (PCBs), phthalates and pyrethroids. It is based on thermal desorption (TD) coupled with gas chromatography/mass spectrometry (GC/MS). Once the thermal desorption conditions were optimized, the method was validated in terms of quantification limits and accuracy using a standard reference material (SRM 2585). Instrumental quantification limits were 10 pg (some OCs, some pyrethroids, musk fragrances, OPs, PAHs, PBDEs and PCBs), 100 pg (phthalates and other OCs) and 1000 pg (other pyrethroids) corresponding respectively to method quantification limits of 1, 10, and 100 pg/m³ for a sampled air volume of 20 m³. Calibration quadratic curves for ranges of 10-1000, 100-10,000, and 1000-100,000 pg, depending on the substance, exhibit determination coefficients above 0.999. Recoveries were between 61 and 96% for chlorinated pesticides, PAHs, PBDEs and PCBs present in the SRM 2585. A test of the method on indoor particulate matter samples (PM₁₀) collected on quartz fiber filters in French dwellings demonstrated its ability to quantify SVOCs from a small amount of PM.

  4. Layer-by-layer self-assembled mutilayer films of gold nanoparticles for surface-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Kawasaki, Hideya; Sugitani, Tsuyoshi; Watanabe, Takehiro; Yonezawa, Tetsu; Moriwaki, Hiroshi; Arakawa, Ryuichi

    2008-10-01

    Layer-by-layer (LBL) self-assembled multilayer films of gold nanoparticles (AuNPs) on a silicon wafer were demonstrated to be promising substrates for surface-assisted laser desorption/ionization (SALDI) mass spectrometry (MS) of peptides and environmental pollutants for the first time. LBL multilayer films, (AuNPs/PAHC)n, consisting of alternating layers of ammonium citrate capped AuNPs and poly(allylamine hydrochloride) (PAHC) were prepared on a silicon surface. Silicon plates with aggregated AuNPs were more suitable than those with dispersed AuNPs for the SALDI-MS of peptides. The number of particle layers had a significant effect on the laser desorption/ionization of angiotensin I; the peak intensity of the peptide (molecular ion amount) increased with an increase in the number of layers of AuNPs. As a result, the (AuNPs/PAHC)5 multilayer films increased the sensitivity of the angiotensin I to subfemtomoles and raised the useful analyte mass range, thus making it possible to detect small proteins (a 12 kDa cytochrome c). The signal enhancement when using (AuNPs/PAHC)5 may be due to (i) the high absorption of the UV laser light at 337 nm by the AuNP layers, (ii) the low thermal conductivity due to the AuNPs being covered with a thin monolayer of PAHC, and (iii) the increase in the surface roughness (approximately 100 nm) with the number of AuNP layers. Thus, laser-induced rapid high heating of AuNPs for effective desorption/ionization of peptides is possible. In addition, it was found that (AuNPs/PAHC)5 could be used to extract environmental pollutants (pyrene and dimethyldistearylammonium chloride) from very dilute aqueous solutions with concentrations less than 10(-10) mg/mL, and the analytes trapped in the LBL film could be identified by introducing the film directly into the SALDI mass spectrometer without needing to elute the analytes out of the film.

  5. A simple and accurate SNP scoring strategy based on typeIIS restriction endonuclease cleavage and matrix-assisted laser desorption/ionization mass spectrometry

    PubMed Central

    Hong, Sun Pyo; Ji, Seung Il; Rhee, Hwanseok; Shin, Soo Kyeong; Hwang, Sun Young; Lee, Seung Hwan; Lee, Soong Deok; Oh, Heung-Bum; Yoo, Wangdon; Kim, Soo-Ok

    2008-01-01

    Background We describe the development of a novel matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF)-based single nucleotide polymorphism (SNP) scoring strategy, termed Restriction Fragment Mass Polymorphism (RFMP) that is suitable for genotyping variations in a simple, accurate, and high-throughput manner. The assay is based on polymerase chain reaction (PCR) amplification and mass measurement of oligonucleotides containing a polymorphic base, to which a typeIIS restriction endonuclease recognition was introduced by PCR amplification. Enzymatic cleavage of the products leads to excision of oligonucleotide fragments representing base variation of the polymorphic site whose masses were determined by MALDI-TOF MS. Results The assay represents an improvement over previous methods because it relies on the direct mass determination of PCR products rather than on an indirect analysis, where a base-extended or fluorescent report tag is interpreted. The RFMP strategy is simple and straightforward, requiring one restriction digestion reaction following target amplification in a single vessel. With this technology, genotypes are generated with a high call rate (99.6%) and high accuracy (99.8%) as determined by independent sequencing. Conclusion The simplicity, accuracy and amenability to high-throughput screening analysis should make the RFMP assay suitable for large-scale genotype association study as well as clinical genotyping in laboratories. PMID:18538037

  6. Paraffin-wax-coated plates as matrix-assisted laser desorption/ionization sample support for high-throughput identification of proteins by peptide mass fingerprinting.

    PubMed

    Tannu, Nilesh S; Wu, Jian; Rao, Vamshi K; Gadgil, Himanshu S; Pabst, Michael J; Gerling, Ivan C; Raghow, Rajendra

    2004-04-15

    We compared trysin-digested protein samples desalted by ZipTip(C18) reverse-phase microcolumns with on-plate washing of peptides deposited either on paraffin-coated plates (PCP), Teflon-based AnchorChip plates, or stainless steel plates, before analysis by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS). Trypsinized bovine serum albumin and ovalbumin and 16 protein spots extracted from silver-stained two-dimensional gels of murine C(2)C(12) myoblasts or human leukocytes, prepared by the above two methods, were subjected to MALDI on PCP, AnchorChip plates, or uncoated stainless steel plates. Although most peptide mass peaks were identical regardless of the method of desalting and concentrating of protein samples, samples washed and concentrated by the PCP-based method had peptide peaks that were not seen in the samples prepared using the ZipTip(C18) columns. The mass spectra of peptides desalted and washed on uncoated stainless steel MALDI plates were consistently inferior due to loss of peptides. Some peptides of large molecular masses were apparently lost from samples desalted by ZipTip(C18) microcolumns, thus diminishing the quality of the fingerprint needed for protein identification. We demonstrate that the method of washing of protein samples on paraffin-coated plates provides an easy, reproducible, inexpensive, and high-throughput alternative to ZipTip(C18)-based purification of protein prior to MALDI-TOF-MS analysis.

  7. Evaluation of the Bruker Biotyper Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry System for Identification of Blood Isolates of Vibrio Species

    PubMed Central

    Cheng, Wern-Cherng; Jan, I-Shiow; Chen, Jong-Min; Teng, Shih-Hua; Teng, Lee-Jene; Sheng, Wang-Huei; Ko, Wen-Chien

    2015-01-01

    Among 56 blood isolates of Vibrio species identified by sequencing analysis of 16S rRNA and rpoB genes, the Bruker Biotyper matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) system correctly identified all isolates of Vibrio vulnificus (n = 20), V. parahaemolyticus (n = 2), and V. fluvialis (n = 1) but none of the isolates of serogroup non-O1/O139 (non-serogroup O1, non-O139) V. cholerae (n = 33) to the species level. All of these serogroup non-O1/O139 V. cholerae isolates were correctly identified using the newly created MALDI-TOF MS database. PMID:25740773

  8. Metabolomic Analysis of Oxidative and Glycolytic Skeletal Muscles by Matrix-Assisted Laser Desorption/IonizationMass Spectrometric Imaging (MALDI MSI)

    NASA Astrophysics Data System (ADS)

    Tsai, Yu-Hsuan; Garrett, Timothy J.; Carter, Christy S.; Yost, Richard A.

    2015-06-01

    Skeletal muscles are composed of heterogeneous muscle fibers that have different physiological, morphological, biochemical, and histological characteristics. In this work, skeletal muscles extensor digitorum longus, soleus, and whole gastrocnemius were analyzed by matrix-assisted laser desorption/ionization mass spectrometry to characterize small molecule metabolites of oxidative and glycolytic muscle fiber types as well as to visualize biomarker localization. Multivariate data analysis such as principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) were performed to extract significant features. Different metabolic fingerprints were observed from oxidative and glycolytic fibers. Higher abundances of biomolecules such as antioxidant anserine as well as acylcarnitines were observed in the glycolytic fibers, whereas taurine and some nucleotides were found to be localized in the oxidative fibers.

  9. Metabolomic Analysis of Oxidative and Glycolytic Skeletal Muscles by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometric Imaging (MALDI MSI)

    PubMed Central

    Tsai, Yu-Hsuan; Garrett, Timothy J.; Carter, Christy S.; Yost, Richard A.

    2015-01-01

    Skeletal muscles are composed of heterogeneous muscle fibers that have different physiological, morphological, biochemical, and histological characteristics. In this work, skeletal muscles extensor digitorum longus, soleus, and whole gastrocnemius were analyzed by matrix-assisted laser desorption/ionization mass spectrometry to characterize small molecule metabolites of oxidative and glycolytic muscle fiber types as well as to visualize biomarker localization. Multivariate data analysis such as principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) were performed to extract significant features. Different metabolic fingerprints were observed from oxidative and glycolytic fibers. Higher abundances of biomolecules such as antioxidant anserine as well as acylcarnitines were observed in the glycolytic fibers, whereas taurine and some nucleotides were found to be localized in the oxidative fibers. PMID:25893271

  10. Nanostructured indium tin oxide slides for small-molecule profiling and imaging mass spectrometry of metabolites by surface-assisted laser desorption ionization MS.

    PubMed

    López de Laorden, Carlos; Beloqui, Ana; Yate, Luis; Calvo, Javier; Puigivila, Maria; Llop, Jordi; Reichardt, Niels-Christian

    2015-01-01

    Due to their electrical conductivity and optical transparency, slides coated with a thin layer of indium tin oxide (ITO) are the standard substrate for protein imaging mass spectrometry on tissue samples by MALDI-TOF MS. We have now studied the rf magnetron sputtering deposition parameters to prepare ITO thin films on glass substrates with the required nanometric surface structure for their use in the matrix-free imaging of metabolites and small-molecule drugs, without affecting the transparency required for classical histology. The custom-made surfaces were characterized by atomic force microscopy, scanning electron microscopy, ellipsometry, UV, and laser desorption ionization MS (LDI-MS) and employed for the LDI-MS-based analysis of glycans and druglike molecules, the quantification of lactose in milk by isotopic dilution, and metabolite imaging on mouse brain tissue samples. PMID:25411795

  11. Combined Fourier-transform infrared imaging and desorption electrospray-ionization linear ion-trap mass spectrometry for analysis of counterfeit antimalarial tablets.

    PubMed

    Ricci, Camilla; Nyadong, Leonard; Fernandez, Facundo M; Newton, Paul N; Kazarian, Sergei G

    2007-01-01

    This paper reports use of a combination of Fourier-transform infrared (FTIR) spectroscopic imaging and desorption electrospray ionization linear ion-trap mass spectrometry (DESI MS) for characterization of counterfeit pharmaceutical tablets. The counterfeit artesunate antimalarial tablets were analyzed by both techniques. The results obtained revealed the ability of FTIR imaging in non-destructive micro-attenuated total reflection (ATR) mode to detect the distribution of all components in the tablet, the identities of which were confirmed by DESI MS. Chemical images of the tablets were obtained with high spatial resolution. The FTIR spectroscopic imaging method affords inherent chemical specificity with rapid acquisition of data. DESI MS enables high-sensitivity detection of trace organic compounds. Combination of these two orthogonal surface-characterization methods has great potential for detection and analysis of counterfeit tablets in the open air and without sample preparation.

  12. Matrix assisted laser desorption/ionization-mass spectrometry imaging (MALDI-MSI) for direct visualization of plant metabolites in situ

    SciTech Connect

    Sturtevant, Drew; Lee, Young -Jin; Chapman, Kent D.

    2015-11-22

    Direct visualization of plant tissues by matrix assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) has revealed key insights into the localization of metabolites in situ. Recent efforts have determined the spatial distribution of primary and secondary metabolites in plant tissues and cells. Strategies have been applied in many areas of metabolism including isotope flux analyses, plant interactions, and transcriptional regulation of metabolite accumulation. Technological advances have pushed achievable spatial resolution to subcellular levels and increased instrument sensitivity by several orders of magnitude. Furthermore, it is anticipated that MALDI-MSI and other MSI approaches will bring a new level of understanding to metabolomics as scientists will be encouraged to consider spatial heterogeneity of metabolites in descriptions of metabolic pathway regulation.

  13. Direct thermal desorption in the analysis of cheese volatiles by gas chromatography and gas chromatography-mass spectrometry: comparison with simultaneous distillation-extraction and dynamic headspace.

    PubMed

    Valero, E; Sanz, J; Martínez-Castro, I

    2001-06-01

    Direct thermal desorption (DTD) has been used as a technique for extracting volatile components of cheese as a preliminary step to their gas chromatographic (GC) analysis. In this study, it is applied to different cheese varieties: Camembert, blue, Chaumes, and La Serena. Volatiles are also extracted using other techniques such as simultaneous distillation-extraction and dynamic headspace. Separation and identification of the cheese components are carried out by GC-mass spectrometry. Approximately 100 compounds are detected in the examined cheeses. The described results show that DTD is fast, simple, and easy to automate; requires only a small amount of sample (approximately 50 mg); and affords quantitative information about the main groups of compounds present in cheeses.

  14. Preparation of porous styrenics-based monolithic layers for thin layer chromatography coupled with matrix-assisted laser-desorption/ionization time-of-flight mass spectrometric detection.

    PubMed

    Lv, Yongqin; Lin, Zhixing; Tan, Tianwei; Svec, Frantisek

    2013-11-01

    Monolithic 50 μm thin poly(4-methylstyrene-co-chloromethylstyrene-co-divinylbenzene) layers attached to 6.0 cm × 3.3 cm glass plates have been prepared, using a thermally initiated polymerization process. These layers had a well-defined porous structure with a globular morphology demonstrated with SEM images and exhibited superhydrophobic properties characterized with a water contact angle of 157°. They were then used for thin-layer chromatography of peptides and proteins fluorescently labeled with fluorescamine. The spots of individual separated compounds were visualized using UV light, and their identities were confirmed with a matrix-assisted laser desorption/ionization time of flight mass spectrometry. The presence of chloromethylstyrene units in the polymer enabled hypercrosslinking via a Friedel-Crafts alkylation reaction, and led to monoliths with much larger surface areas, which were suitable for separations of small dye molecules.

  15. Rapid inactivation of Mycobacterium and nocardia species before identification using matrix-assisted laser desorption ionization-time of flight mass spectrometry.

    PubMed

    Dunne, W Michael; Doing, Kirk; Miller, Elizabeth; Miller, Eric; Moreno, Erik; Baghli, Mehdi; Mailler, Sandrine; Girard, Victoria; van Belkum, Alex; Deol, Parampal

    2014-10-01

    The identification of mycobacteria outside biocontainment facilities requires that the organisms first be rendered inactive. Exposure to 70% ethanol (EtOH) either before or after mechanical disruption was evaluated in order to establish a safe, effective, and rapid inactivation protocol that is compatible with identification of Mycobacterium and Nocardia species using matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS). A combination of 5 min of bead beating in 70% EtOH followed by a 10-min room temperature incubation period was found to be rapidly bactericidal and provided high-quality spectra compared to spectra obtained directly from growth on solid media. The age of the culture, the stability of the refrigerated or frozen lysates, and freeze-thaw cycles did not adversely impact the quality of the spectra or the identification obtained.

  16. Thermal transformation of bioactive caffeic acid on fumed silica seen by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry and quantum chemical methods.

    PubMed

    Kulik, Tetiana V; Lipkovska, Natalia O; Barvinchenko, Valentyna M; Palyanytsya, Borys B; Kazakova, Olga A; Dudik, Olesia O; Menyhárd, Alfréd; László, Krisztina

    2016-05-15

    Thermochemical studies of hydroxycinnamic acid derivatives and their surface complexes are important for the pharmaceutical industry, medicine and for the development of technologies of heterogeneous biomass pyrolysis. In this study, structural and thermal transformations of caffeic acid complexes on silica surfaces were studied by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry (TPD MS) and quantum chemical methods. Two types of caffeic acid surface complexes are found to form through phenolic or carboxyl groups. The kinetic parameters of the chemical reactions of caffeic acid on silica surface are calculated. The mechanisms of thermal transformations of the caffeic chemisorbed surface complexes are proposed. Thermal decomposition of caffeic acid complex chemisorbed through grafted ester group proceeds via three parallel reactions, producing ketene, vinyl and acetylene derivatives of 1,2-dihydroxybenzene. Immobilization of phenolic acids on the silica surface improves greatly their thermal stability.

  17. Determination of bacterial protein profiles by matrix-assisted laser desorption/ionization mass spectrometry with high-performance liquid chromatography.

    PubMed

    Liang, X; Zheng, K; Qian, M G; Lubman, D M

    1996-01-01

    A rapid method for profiling bacterial and cellular proteins has been developed using a combination of capillary high-performance liquid chromatography separation followed by (MALDI-MS) matrix-assisted laser desorption/ionization mass spectrometric analysis. In this method, bacteria are sonicated, the cell walls broken, and the water-soluble proteins precipitated for analysis. The proteins are separated by capillary liquid chromatography and detected on-line by a UV absorption detector. The eluents are then collected for off-line analysis by MALDI-MS. Using this method, it is demonstrated that bacteria can be discriminated based upon their protein profiles to the species level with only pmol level detection of proteins. It has also proved to be a fast and accurate means for monitoring the expression of Hsp27 in an insect cell system.

  18. Microbial Typing by Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry: Do We Need Guidance for Data Interpretation?

    PubMed Central

    van Belkum, Alex; Goering, Richard V.; Girard, Victoria; Welker, Martin; Van Nuenen, Marc; Pincus, David H.; Arsac, Maud; Durand, Géraldine

    2014-01-01

    The integration of matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) in clinical microbiology has revolutionized species identification of bacteria, yeasts, and molds. However, beyond straightforward identification, the method has also been suggested to have the potential for subspecies-level or even type-level epidemiological analyses. This minireview explores MALDI-TOF MS-based typing, which has already been performed on many clinically relevant species. We discuss the limits of the method's resolution and we suggest interpretative criteria allowing valid comparison of strain-specific data. We conclude that guidelines for MALDI-TOF MS-based typing can be developed along the same lines as those used for the interpretation of data from pulsed-field gel electrophoresis (PFGE). PMID:25056329

  19. Micro-solid-phase extraction coupled to desorption electrospray ionization-high-resolution mass spectrometry for the analysis of explosives in soil.

    PubMed

    Bianchi, Federica; Gregori, Adolfo; Braun, Gabriele; Crescenzi, Carlo; Careri, Maria

    2015-01-01

    Home-made micro-solid-phase extraction (SPE) cartridges using different adsorbent materials were tested for the desorption electrospray ionization-high-resolution mass spectrometry (DESI-HRMS) determination of explosives like 2,4,6-trinitrotoluene, cyclotrimethylene-trinitramine, cyclotetramethylene-tetranitramine, pentaerythritol tetranitrate, and trinitrophenylmethylnitramine in soil samples. Quantitation limits in the low nanogram per kilogram range proved the reliability of the method for the detection of explosives at ultra-trace levels. The reduced sample preparation allowed for low costs and high-throughput analyses. Finally, the superior extraction capability of the method was proved by obtaining DESI-HRMS responses at least five times higher than those achieved by performing DESI-HRMS analyses of solid-liquid extracts spotted onto commercial polytetrafluoroethylene slides.

  20. The development of a matrix-assisted laser desorption/ionization mass spectrometry-based method for the protein fingerprinting and identification of Aeromonas species using whole cells.

    PubMed

    Donohue, Maura J; Smallwood, Anthony W; Pfaller, Stacy; Rodgers, Mark; Shoemaker, Jody A

    2006-06-01

    This report describes the development of a method to detect the waterborne pathogen Aeromonas using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The genus Aeromonas is one of several medically significant genera that have gained prominence due to their evolving taxonomy and controversial role in human diseases. In this study, MALDI-MS was applied to the characterization of seventeen species of Aeromonas. These seventeen species were represented by thirty-two strains, which included type, reference and clinical isolates. Intact cells from each strain were used to generate a reproducible library of protein mass spectral fingerprints or m/z signatures. Under the test conditions used, peak lists of the mass ions observed in each species revealed that three mass ions were conserved among all the seventeen species tested. These common mass ions having an average m/z of 6301, 12,160 or 12,254, and 13,450, can be potentially used as genus-specific biomarkers to identify Aeromonas in unknown samples. A dendrogram generated using the m/z signatures of all the strains tested indicated that the mass spectral data contained sufficient information to distinguish between genera, species, and strains. There are several advantages of using MALDI-MS based protein mass spectral fingerprinting of whole cells for the identification of microorganisms as well as for their differentiation at the sub-species level: (1) the capability to detect proteins, (2) high throughput, and (3) relatively simple sample preparation techniques. The accuracy and speed with which data can be obtained makes MALDI-MS a powerful tool especially suited for environmental monitoring and detection of biological hazards.

  1. Tailor-Made Stable Zr(IV)-Based Metal-Organic Frameworks for Laser Desorption/Ionization Mass Spectrometry Analysis of Small Molecules and Simultaneous Enrichment of Phosphopeptides.

    PubMed

    Chen, Lianfang; Ou, Junjie; Wang, Hongwei; Liu, Zhongshan; Ye, Mingliang; Zou, Hanfa

    2016-08-10

    Although thousands of metal-organic frameworks (MOFs) have been fabricated and widely applied in gas storage/separations, adsorption, catalysis, and so on, few kinds of MOFs have been used as adsorption materials while simultaneously serving as matrixes to analyze small molecules for laser desorption/ionization mass spectrometry (LDI-MS). Herein, a new concept is introduced to design and synthesize MOFs as both adsorption materials and matrixes according to the structure of ligands and common matrixes. The proof of concept design was demonstrated by selection of 2,5-pyridinedicarboxylic acid (PDC) and 2,5-dihydroxyterephthalic acid (DHT) as ligands for synthesis of MOFs. Two Zr(IV)-based MOFs of UiO-66-PDC and UiO-66-(OH)2 were synthesized and applied for the first time as new matrixes for analysis of small molecules by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Both of them showed low matrix interferences, high ionization efficiency, and good reproducibility when used as matrixes. A variety of small molecules, including saccharides, amino acids, nucleosides, peptides, alkaline drugs, and natural products, were analyzed. In addition, UiO-66-(OH)2 exhibited potential for application in the quantitative determination of glucose and pyridoxal 5'-phosphate. Furthermore, thanks to its intrinsically large surface area and highly ordered pores, UiO-66-(OH)2 also showed sensitive and specific enrichment of phosphopeptides prior to MS analysis. These results demonstrated that this strategy can be used to efficiently screen tailor-made MOFs as matrixes to analyze small molecules by MALDI-TOF-MS. PMID:27427857

  2. IN-SITU PROBING OF RADIATION-INDUCED PROCESSING OF ORGANICS IN ASTROPHYSICAL ICE ANALOGS-NOVEL LASER DESORPTION LASER IONIZATION TIME-OF-FLIGHT MASS SPECTROSCOPIC STUDIES

    SciTech Connect

    Gudipati, Murthy S.; Yang Rui E-mail: ryang73@ustc.edu

    2012-09-01

    Understanding the evolution of organic molecules in ice grains in the interstellar medium (ISM) under cosmic rays, stellar radiation, and local electrons and ions is critical to our understanding of the connection between ISM and solar systems. Our study is aimed at reaching this goal of looking directly into radiation-induced processing in these ice grains. We developed a two-color laser-desorption laser-ionization time-of-flight mass spectroscopic method (2C-MALDI-TOF), similar to matrix-assisted laser desorption and ionization time-of-flight (MALDI-TOF) mass spectroscopy. Results presented here with polycyclic aromatic hydrocarbon (PAH) probe molecules embedded in water-ice at 5 K show for the first time that hydrogenation and oxygenation are the primary chemical reactions that occur in astrophysical ice analogs when subjected to Ly{alpha} radiation. We found that hydrogenation can occur over several unsaturated bonds and the product distribution corresponds to their stabilities. Multiple hydrogenation efficiency is found to be higher at higher temperatures (100 K) compared to 5 K-close to the interstellar ice temperatures. Hydroxylation is shown to have similar efficiencies at 5 K or 100 K, indicating that addition of O atoms or OH radicals to pre-ionized PAHs is a barrierless process. These studies-the first glimpses into interstellar ice chemistry through analog studies-show that once accreted onto ice grains PAHs lose their PAH spectroscopic signatures through radiation chemistry, which could be one of the reason for the lack of PAH detection in interstellar ice grains, particularly the outer regions of cold, dense clouds or the upper molecular layers of protoplanetary disks.

  3. Correlated matrix-assisted laser desorption/ionization mass spectrometry and fluorescent imaging of photocleavable peptide-coded random bead-arrays

    PubMed Central

    Lim, Mark J; Liu, Ziying; Braunschweiger, Karen I; Awad, Amany; Rothschild, Kenneth J

    2013-01-01

    RATIONALE Rapidly performing global proteomic screens is an important goal in the post-genomic era. Correlated matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and fluorescent imaging of photocleavable peptide-coded random bead-arrays was evaluated as a critical step in a new method for proteomic screening that combines many of the advantages of MS with fluorescence-based microarrays. METHODS Small peptide-coded model bead libraries containing up to 20 different bead species were constructed by attaching peptides to 30–34 µm diameter glass, agarose or TentaGel® beads using photocleavable biotin or a custom-designed photocleavable linker. The peptide-coded bead libraries were randomly arrayed into custom gold-coated micro-well plates with 45 µm diameter wells and subjected to fluorescence and MALDI mass spectrometric imaging (MALDI-MSI). RESULTS Photocleavable mass-tags from individual beads in these libraries were spatially localized as ∼65 µm spots using MALDI-MSI with high sensitivity and mass resolution. Fluorescently tagged beads were identified and correlated with their matching photocleavable mass-tags by comparing the fluorescence and MALDI-MS images of the same bead-array. Post-translational modification of the peptide Kemptide was also detected on individual beads in a photocleavable peptide-coded bead-array by MALDI-MSI alone, after exposure of the beads to protein kinase A (PKA). CONCLUSIONS Correlated MALDI-MS and fluorescent imaging of photocleavable peptide-coded random bead-arrays can provide a basis for performing global proteomic screening. © 2013 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons, Ltd. PMID:24285390

  4. Rapid Characterization of Microalgae and Microalgae Mixtures Using Matrix-Assisted Laser Desorption Ionization Time-Of-Flight Mass Spectrometry (MALDI-TOF MS).

    PubMed

    Barbano, Duane; Diaz, Regina; Zhang, Lin; Sandrin, Todd; Gerken, Henri; Dempster, Thomas

    2015-01-01

    Current molecular methods to characterize microalgae are time-intensive and expensive. Matrix Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) may represent a rapid and economical alternative approach. The objectives of this study were to determine whether MALDI-TOF MS can be used to: 1) differentiate microalgae at the species and strain levels and 2) characterize simple microalgal mixtures. A common protein extraction sample preparation method was used to facilitate rapid mass spectrometry-based analysis of 31 microalgae. Each yielded spectra containing between 6 and 56 peaks in the m/z 2,000 to 20,000 range. The taxonomic resolution of this approach appeared higher than that of 18S rDNA sequence analysis. For example, two strains of Scenedesmus acutus differed only by two 18S rDNA nucleotides, but yielded distinct MALDI-TOF mass spectra. Mixtures of two and three microalgae yielded relatively complex spectra that contained peaks associated with members of each mixture. Interestingly, though, mixture-specific peaks were observed at m/z 11,048 and 11,230. Our results suggest that MALDI-TOF MS affords rapid characterization of individual microalgae and simple microalgal mixtures.

  5. Determination of the disulfide bond arrangement of human respiratory syncytial virus attachment (G) protein by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed Central

    Gorman, J. J.; Ferguson, B. L.; Speelman, D.; Mills, J.

    1997-01-01

    The attachment protein or G protein of the A2 strain of human respiratory syncytial virus (RSV) was digested with trypsin and the resultant peptides separated by reverse-phase high-performance liquid chromatography (HPLC). One tryptic peptide produced a mass by matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS) corresponding to residues 152-187 with the four Cys residues of the ectodomain (residues 173, 176, 182, and 186) in disulfide linkage and absence of glycosylation. Sub-digestion of this tryptic peptide with pepsin and thermolysin produced peptides consistent with disulfide bonds between Cys173 and Cys186 and between Cys176 and Cys182. Analysis of ions produced by post-source decay of a peptic peptide during MALDI-TOF-MS revealed fragmentation of peptide bonds with minimal fission of an inter-chain disulfide bond. Ions produced by this unprecedented MALDI-induced post-source fragmentation corroborated the existence of the disulfide arrangement deduced from mass analysis of proteolysis products. These findings indicate that the ectodomain of the G protein has a non-glycosylated subdomain containing a "cystine noose." PMID:9194191

  6. Assessment of a new method for the analysis of decomposition gases of polymers by a combining thermogravimetric solid-phase extraction and thermal desorption gas chromatography mass spectrometry.

    PubMed

    Duemichen, E; Braun, U; Senz, R; Fabian, G; Sturm, H

    2014-08-01

    For analysis of the gaseous thermal decomposition products of polymers, the common techniques are thermogravimetry, combined with Fourier transformed infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). These methods offer a simple approach to the decomposition mechanism, especially for small decomposition molecules. Complex spectra of gaseous mixtures are very often hard to identify because of overlapping signals. In this paper a new method is described to adsorb the decomposition products during controlled conditions in TGA on solid-phase extraction (SPE) material: twisters. Subsequently the twisters were analysed with thermal desorption gas chromatography mass spectrometry (TDS-GC-MS), which allows the decomposition products to be separated and identified using an MS library. The thermoplastics polyamide 66 (PA 66) and polybutylene terephthalate (PBT) were used as example polymers. The influence of the sample mass and of the purge gas flow during the decomposition process was investigated in TGA. The advantages and limitations of the method were presented in comparison to the common analysis techniques, TGA-FTIR and TGA-MS.

  7. Petroleomic Analysis of Bio- Oils from the Fast Pyrolysis or Biomass: Laser Desorption Ionization-Linear Ion Trap-Orbitrap mass Spectrometry Approach

    SciTech Connect

    Smith, Erica A.; Lee, Young Jin

    2010-08-23

    Fast pyrolysis of biomass produces bio-oils that can be upgraded into biofuels. Despite similar physical properties to petroleum, the chemical properties of bio-oils are quite different and their chemical compositions, particularly those of non-volatile compounds, are not well-known. Here, we report the first time attempt at analyzing bio-oils using high-resolution mass spectrometry (MS), which employed laser desorption ionization-linear ion trap-Orbitrap MS. Besides a few limitations, we could determine chemical compositions for over 100 molecular compounds in a bio-oil sample produced from the pyrolysis of a loblolly pine tree. These compounds consist of 3-6 oxygens and 9-17 double-bond equivalents (DBEs). Among those, O{sub 4} compounds with a DBE of 9-13 were most abundant. Unlike petroleum oils, the lack of nearby molecules within a {+-}2 Da mass window for major components enabled clear isolation of precursor ions for subsequent MS/MS structural investigations. Petroleomic analysis and a comparison to low-mass components in hydrolytic lignin suggest that they are dimers and trimers of depolymerized lignin.

  8. Rapid Characterization of Microalgae and Microalgae Mixtures Using Matrix-Assisted Laser Desorption Ionization Time-Of-Flight Mass Spectrometry (MALDI-TOF MS)

    PubMed Central

    Barbano, Duane; Diaz, Regina; Zhang, Lin; Sandrin, Todd; Gerken, Henri; Dempster, Thomas

    2015-01-01

    Current molecular methods to characterize microalgae are time-intensive and expensive. Matrix Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) may represent a rapid and economical alternative approach. The objectives of this study were to determine whether MALDI-TOF MS can be used to: 1) differentiate microalgae at the species and strain levels and 2) characterize simple microalgal mixtures. A common protein extraction sample preparation method was used to facilitate rapid mass spectrometry-based analysis of 31 microalgae. Each yielded spectra containing between 6 and 56 peaks in the m/z 2,000 to 20,000 range. The taxonomic resolution of this approach appeared higher than that of 18S rDNA sequence analysis. For example, two strains of Scenedesmus acutus differed only by two 18S rDNA nucleotides, but yielded distinct MALDI-TOF mass spectra. Mixtures of two and three microalgae yielded relatively complex spectra that contained peaks associated with members of each mixture. Interestingly, though, mixture-specific peaks were observed at m/z 11,048 and 11,230. Our results suggest that MALDI-TOF MS affords rapid characterization of individual microalgae and simple microalgal mixtures. PMID:26271045

  9. Differentiation of prostate cancer from normal tissue in radical prostatectomy specimens by desorption electrospray ionization and touch spray ionization mass spectrometry.

    PubMed

    Kerian, K S; Jarmusch, A K; Pirro, V; Koch, M O; Masterson, T A; Cheng, L; Cooks, R G

    2015-02-21

    Radical prostatectomy is a common treatment option for prostate cancer before it has spread beyond the prostate. Examination for surgical margins is performed post-operatively with positive margins reported to occur in 6.5-32% of cases. Rapid identification of cancerous tissue during surgery could improve surgical resection. Desorption electrospray ionization (DESI) is an ambient ionization method which produces mass spectra dominated by lipid signals directly from prostate tissue. With the use of multivariate statistics, these mass spectra can be used to differentiate cancerous and normal tissue. The method was applied to 100 samples from 12 human patients to create a training set of MS data. The quality of the discrimination achieved was evaluated using principal component analysis - linear discriminant analysis (PCA-LDA) and confirmed by histopathology. Cross validation (PCA-LDA) showed >95% accuracy. An even faster and more convenient method, touch spray (TS) mass spectrometry, not previously tested to differentiate diseased tissue, was also evaluated by building a similar MS data base characteristic of tumor and normal tissue. An independent set of 70 non-targeted biopsies from six patients was then used to record lipid profile data resulting in 110 data points for an evaluation dataset for TS-MS. This method gave prediction success rates measured against histopathology of 93%. These results suggest that DESI and TS could be useful in differentiating tumor and normal prostate tissue at surgical margins and that these methods should be evaluated intra-operatively.

  10. Nanomanipulation-Coupled Matrix-Assisted Laser Desorption/ Ionization-Direct Organelle Mass Spectrometry: A Technique for the Detailed Analysis of Single Organelles

    NASA Astrophysics Data System (ADS)

    Phelps, Mandy S.; Sturtevant, Drew; Chapman, Kent D.; Verbeck, Guido F.

    2016-02-01

    We describe a novel technique combining precise organelle microextraction with deposition and matrix-assisted laser desorption/ionization (MALDI) for a rapid, minimally invasive mass spectrometry (MS) analysis of single organelles from living cells. A dual-positioner nanomanipulator workstation was utilized for both extraction of organelle content and precise co-deposition of analyte and matrix solution for MALDI-direct organelle mass spectrometry (DOMS) analysis. Here, the triacylglycerol (TAG) profiles of single lipid droplets from 3T3-L1 adipocytes were acquired and results validated with nanoelectrospray ionization (NSI) MS. The results demonstrate the utility of the MALDI-DOMS technique as it enabled longer mass analysis time, higher ionization efficiency, MS imaging of the co-deposited spot, and subsequent MS/MS capabilities of localized lipid content in comparison to NSI-DOMS. This method provides selective organellar resolution, which complements current biochemical analyses and prompts for subsequent subcellular studies to be performed where limited samples and analyte volume are of concern.

  11. Dithranol as a matrix for matrix assisted laser desorption/ionization imaging on a fourier transform ion cyclotron resonance mass spectrometer.

    PubMed

    Le, Cuong H; Han, Jun; Borchers, Christoph H

    2013-11-26

    Mass spectrometry imaging (MSI) determines the spatial localization and distribution patterns of compounds on the surface of a tissue section, mainly using MALDI (matrix assisted laser desorption/ionization)-based analytical techniques. New matrices for small-molecule MSI, which can improve the analysis of low-molecular weight (MW) compounds, are needed. These matrices should provide increased analyte signals while decreasing MALDI background signals. In addition, the use of ultrahigh-resolution instruments, such as Fourier transform ion cyclotron resonance (FTICR) mass spectrometers, has the ability to resolve analyte signals from matrix signals, and this can partially overcome many problems associated with the background originating from the MALDI matrix. The reduction in the intensities of the metastable matrix clusters by FTICR MS can also help to overcome some of the interferences associated with matrix peaks on other instruments. High-resolution instruments such as the FTICR mass spectrometers are advantageous as they can produce distribution patterns of many compounds simultaneously while still providing confidence in chemical identifications. Dithranol (DT; 1,8-dihydroxy-9,10-dihydroanthracen-9-one) has previously been reported as a MALDI matrix for tissue imaging. In this work, a protocol for the use of DT for MALDI imaging of endogenous lipids from the surfaces of mammalian tissue sections, by positive-ion MALDI-MS, on an ultrahigh-resolution hybrid quadrupole FTICR instrument has been provided.

  12. Direct identification of trypanosomatids by matrix-assisted laser desorption ionization-time of flight mass spectrometry (DIT MALDI-TOF MS).

    PubMed

    Avila, C C; Almeida, F G; Palmisano, G

    2016-08-01

    Accurate and rapid determination of trypanosomatids is essential in epidemiological surveillance and therapeutic studies. Matrix-assisted laser desorption ionization/time of flight mass spectrometry (MALDI-TOF MS) has been shown to be a useful and powerful technique to identify bacteria, fungi, metazoa and human intact cells with applications in clinical settings. Here, we developed and optimized a MALDI-TOF MS method to profile trypanosomatids. trypanosomatid cells were deposited on a MALDI target plate followed by addition of matrix solution. The plate was then subjected to MALDI-TOF MS measurement to create reference mass spectra library and unknown samples were identified by pattern matching using the BioTyper software tool. Several m/z peaks reproducibly and uniquely identified trypanosomatids species showing the potentials of direct identification of trypanosomatids by MALDI-TOF MS. Moreover, this method discriminated different life stages of Trypanosoma cruzi, epimastigote and bloodstream trypomastigote and Trypanosoma brucei, procyclic and bloodstream. T. cruzi Discrete Typing Units (DTUs) were also discriminated in three clades. However, it was not possible to achieve enough resolution and software-assisted identification at the strain level. Overall, this study shows the importance of MALDI-TOF MS for the direct identification of trypanosomatids and opens new avenues for mass spectrometry-based detection of parasites in biofluids. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27659938

  13. Dithranol as a Matrix for Matrix Assisted Laser Desorption/Ionization Imaging on a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

    PubMed Central

    Le, Cuong H.; Han, Jun; Borchers, Christoph H.

    2013-01-01

    Mass spectrometry imaging (MSI) determines the spatial localization and distribution patterns of compounds on the surface of a tissue section, mainly using MALDI (matrix assisted laser desorption/ionization)-based analytical techniques. New matrices for small-molecule MSI, which can improve the analysis of low-molecular weight (MW) compounds, are needed. These matrices should provide increased analyte signals while decreasing MALDI background signals. In addition, the use of ultrahigh-resolution instruments, such as Fourier transform ion cyclotron resonance (FTICR) mass spectrometers, has the ability to resolve analyte signals from matrix signals, and this can partially overcome many problems associated with the background originating from the MALDI matrix. The reduction in the intensities of the metastable matrix clusters by FTICR MS can also help to overcome some of the interferences associated with matrix peaks on other instruments. High-resolution instruments such as the FTICR mass spectrometers are advantageous as they can produce distribution patterns of many compounds simultaneously while still providing confidence in chemical identifications. Dithranol (DT; 1,8-dihydroxy-9,10-dihydroanthracen-9-one) has previously been reported as a MALDI matrix for tissue imaging. In this work, a protocol for the use of DT for MALDI imaging of endogenous lipids from the surfaces of mammalian tissue sections, by positive-ion MALDI-MS, on an ultrahigh-resolution hybrid quadrupole FTICR instrument has been provided. PMID:24300588

  14. Direct bacterial profiling by matrix-assisted laser desorption-ionization time-of-flight mass spectrometry for identification of pathogenic Neisseria.

    PubMed

    Ilina, Elena N; Borovskaya, Alexandra D; Malakhova, Maja M; Vereshchagin, Vladimir A; Kubanova, Anna A; Kruglov, Alexander N; Svistunova, Tatyana S; Gazarian, Anaida O; Maier, Thomas; Kostrzewa, Markus; Govorun, Vadim M

    2009-01-01

    The present study investigates the suitability of direct bacterial profiling as a tool for the identification and subtyping of pathogenic Neisseria. The genus Neisseria includes two human pathogens, Neisseria meningitidis and Neisseria gonorrhoeae, as well as several nonpathogenic Neisseria species. Here, a matrix-assisted laser desorption/ionization time-of-flight mass spectrometry profiling protocol was optimized using a laboratory strain of E. coli DH5alpha to guarantee high quality and reproducible results. Subsequently, mass spectra for both laboratory and clinical strains of N. gonorrhoeae, N. meningitidis, and several nonpathogenic Neisseria species were collected. Significant interspecies differences but little intraspecies diversity were revealed by means of a visual inspection and bioinformatics examination using the MALDI BioTyper software. Cluster analysis successfully separated mass spectra collected from three groups that corresponded to N. gonorrhoeae, N. meningitidis, and nonpathogenic Neisseria isolates. Requiring only one bacterial colony for testing and using a fast and easy measuring protocol, this approach represents a powerful tool for the rapid identification of pathogenic Neisseria and can be adopted for other microorganisms.

  15. Negative Ion In-Source Decay Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry for Sequencing Acidic Peptides

    NASA Astrophysics Data System (ADS)

    McMillen, Chelsea L.; Wright, Patience M.; Cassady, Carolyn J.

    2016-05-01

    Matrix-assisted laser desorption/ionization (MALDI) in-source decay was studied in the negative ion mode on deprotonated peptides to determine its usefulness for obtaining extensive sequence information for acidic peptides. Eight biological acidic peptides, ranging in size from 11 to 33 residues, were studied by negative ion mode ISD (nISD). The matrices 2,5-dihydroxybenzoic acid, 2-aminobenzoic acid, 2-aminobenzamide, 1,5-diaminonaphthalene, 5-amino-1-naphthol, 3-aminoquinoline, and 9-aminoacridine were used with each peptide. Optimal fragmentation was produced with 1,5-diaminonphthalene (DAN), and extensive sequence informative fragmentation was observed for every peptide except hirudin(54-65). Cleavage at the N-Cα bond of the peptide backbone, producing c' and z' ions, was dominant for all peptides. Cleavage of the N-Cα bond N-terminal to proline residues was not observed. The formation of c and z ions is also found in electron transfer dissociation (ETD), electron capture dissociation (ECD), and positive ion mode ISD, which are considered to be radical-driven techniques. Oxidized insulin chain A, which has four highly acidic oxidized cysteine residues, had less extensive fragmentation. This peptide also exhibited the only charged localized fragmentation, with more pronounced product ion formation adjacent to the highly acidic residues. In addition, spectra were obtained by positive ion mode ISD for each protonated peptide; more sequence informative fragmentation was observed via nISD for all peptides. Three of the peptides studied had no product ion formation in ISD, but extensive sequence informative fragmentation was found in their nISD spectra. The results of this study indicate that nISD can be used to readily obtain sequence information for acidic peptides.

  16. Top-down proteomic identification of Shiga toxin 2 subtypes from Shiga toxin-producing Escherichia coli by Matrix-Assisted Laser Desorption Ionization-Tandem Time of Flight mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have analyzed 26 Shiga toxin-producing Escherichia coli (STEC) strains for Shiga toxin 2 (Stx2) production using matrix-assisted laser desorption/ionization time-of-flight-time-of-flight tandem mass spectrometry (MALDI-TOF-TOF-MS/MS) and top-down proteomic analysis. STEC strains were induced to ...

  17. Bacteriophage cell lysis of Shiga toxin-producing Escherichia coli for top-down proteomic identification of Shiga toxin 1 & 2 using matrix-assisted laser desorption/ionization tandem time-of-light mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    RATIONALE: Analysis of bacteria by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) often relies upon sample preparation methods that result in cell lysis, e.g. bead-beating. However, Shiga toxin-producing Escherichia coli (STEC) can undergo bacteriophage...

  18. Carbon Dots and 9AA as a Binary Matrix for the Detection of Small Molecules by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry.

    PubMed

    Chen, Yongli; Gao, Dan; Bai, Hangrui; Liu, Hongxia; Lin, Shuo; Jiang, Yuyang

    2016-07-01

    Application of matrix-assisted laser-desorption/ionization mass spectrometry (MALDI MS) to analyze small molecules have some limitations, due to the inhomogeneous analyte/matrix co-crystallization and interference of matrix-related peaks in low m/z region. In this work, carbon dots (CDs) were for the first time applied as a binary matrix with 9-Aminoacridine (9AA) in MALDI MS for small molecules analysis. By 9AA/CDs assisted desorption/ionization (D/I) process, a wide range of small molecules, including nucleosides, amino acids, oligosaccharides, peptides, and anticancer drugs with a higher sensitivity were demonstrated in the positive ion mode. A detection limit down to 5 fmol was achieved for cytidine. 9AA/CDs matrix also exhibited excellent reproducibility compared with 9AA matrix. Moreover, by exploring the ionization mechanism of the matrix, the influence factors might be attributed to the four parts: (1) the strong UV absorption of 9AA/CDs due to their π-conjugated network; (2) the carboxyl groups modified on the CDs surface act as protonation sites for proton transfer in positive ion mode; (3) the thin layer crystal of 9AA/CDs could reach a high surface temperature more easily and lower transfer energy for LDI MS; (4) CDs could serve as a matrix additive to suppress 9AA ionization. Furthermore, this matrix was allowed for the analysis of glucose as well as nucleosides in human urine, and the level of cytidine was quantified with a linear range of 0.05-5 mM (R(2) > 0.99). Therefore, the 9AA/CDs matrix was proven to be an effective MALDI matrix for the analysis of small molecules with improved sensitivity and reproducibility. This work provides an alternative solution for small molecules detection that can be further used in complex samples analysis. Graphical Abstract ᅟ.

  19. Carbon Dots and 9AA as a Binary Matrix for the Detection of Small Molecules by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Chen, Yongli; Gao, Dan; Bai, Hangrui; Liu, Hongxia; Lin, Shuo; Jiang, Yuyang

    2016-07-01

    Application of matrix-assisted laser-desorption/ionization mass spectrometry (MALDI MS) to analyze small molecules have some limitations, due to the inhomogeneous analyte/matrix co-crystallization and interference of matrix-related peaks in low m/z region. In this work, carbon dots (CDs) were for the first time applied as a binary matrix with 9-Aminoacridine (9AA) in MALDI MS for small molecules analysis. By 9AA/CDs assisted desorption/ionization (D/I) process, a wide range of small molecules, including nucleosides, amino acids, oligosaccharides, peptides, and anticancer drugs with a higher sensitivity were demonstrated in the positive ion mode. A detection limit down to 5 fmol was achieved for cytidine. 9AA/CDs matrix also exhibited excellent reproducibility compared with 9AA matrix. Moreover, by exploring the ionization mechanism of the matrix, the influence factors might be attributed to the four parts: (1) the strong UV absorption of 9AA/CDs due to their π-conjugated network; (2) the carboxyl groups modified on the CDs surface act as protonation sites for proton transfer in positive ion mode; (3) the thin layer crystal of 9AA/CDs could reach a high surface temperature more easily and lower transfer energy for LDI MS; (4) CDs could serve as a matrix additive to suppress 9AA ionization. Furthermore, this matrix was allowed for the analysis of glucose as well as nucleosides in human urine, and the level of cytidine was quantified with a linear range of 0.05-5 mM (R2 > 0.99). Therefore, the 9AA/CDs matrix was proven to be an effective MALDI matrix for the analysis of small molecules with improved sensitivity and reproducibility. This work provides an alternative solution for small molecules detection that can be further used in complex samples analysis.

  20. Analysis of trace contamination of phthalate esters in ultrapure water using a modified solid-phase extraction procedure and automated thermal desorption-gas chromatography/mass spectrometry.

    PubMed

    Liu, Hsu-Chuan; Den, Walter; Chan, Shu-Fei; Kin, Kuan Tzu

    2008-04-25

    The present study was aimed to develop a procedure modified from the conventional solid-phase extraction (SPE) method for the analysis of trace concentration of phthalate esters in industrial ultrapure water (UPW). The proposed procedure allows UPW sample to be drawn through a sampling tube containing hydrophobic sorbent (Tenax TA) to concentrate the aqueous phthalate esters. The solid trap was then demoisturized by two-stage gas drying before subjecting to thermal desorption and analysis by gas chromatography-mass spectrometry. This process removes the solvent extraction procedure necessary for the conventional SPE method, and permits automation of the analytical procedure for high-volume analyses. Several important parameters, including desorption temperature and duration, packing quantity and demoisturizing procedure, were optimized in this study based on the analytical sensitivity for a standard mixture containing five different phthalate esters. The method detection limits for the five phthalate esters were between 36 ng l(-1) and 95 ng l(-1) and recovery rates between 15% and 101%. Dioctyl phthalate (DOP) was not recovered adequately because the compound was both poorly adsorbed and desorbed on and off Tenax TA sorbents. Furthermore, analyses of material leaching from poly(vinyl chloride) (PVC) tubes as well as the actual water samples showed that di-n-butyl phthalate (DBP) and di(2-ethylhexyl) phthalate (DEHP) were the common contaminants detected from PVC contaminated UPW and the actual UPW, as well as in tap water. The reduction of DEHP in the production processes of actual UPW was clearly observed, however a DEHP concentration of 0.20 microg l(-1) at the point of use was still being quantified, suggesting that the contamination of phthalate esters could present a barrier to the future cleanliness requirement of UPW. The work demonstrated that the proposed modified SPE procedure provided an effective method for rapid analysis and contamination

  1. Dispersive micro solid-phase extraction for the rapid analysis of synthetic polycyclic musks using thermal desorption gas chromatography-mass spectrometry.

    PubMed

    Chung, Wu-Hsun; Tzing, Shin-Hwa; Ding, Wang-Hsien

    2013-09-13

    A simple and solvent-free method for the rapid analysis of five synthetic polycyclic musks in water samples is described. The method involves the use of dispersive micro solid-phase extraction (D-μ-SPE) coupled with direct thermal desorption (TD) gas chromatography-mass spectrometry (GC-MS) operating in the selected-ion-storage (SIS) mode. The parameters affecting the extraction efficiency of the target analytes from water sample and the thermal desorption conditions in the GC injection-port were optimized using a central composite design method. The optimal extraction conditions involved immersing 3.2mg of a typical octadecyl (C18) bonded silica adsorbent (i.e., ENVI-18) in a 10mL water sample. After extraction by vigorously shaking for 1.0min, the adsorbents were collected and dried on a filter. The adsorbents were transferred to a micro-vial, which was directly inserted into GC temperature-programmed injector, and the extracted target analytes were then thermally desorbed in the GC injection-port at 337°C for 3.8min. The limits of quantitation (LOQs) were determined to be 1.2-3.0ng/L. Precision, as indicated by relative standard deviations (RSDs), was less than 9% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 74 and 90%. A preliminary analysis of the river water samples revealed that galaxolide (HHCB) and tonalide (AHTN) were the two most common synthetic polycyclic musks present. Using a standard addition method, their concentrations were determined to in the range from 11 to 140ng/L.

  2. Magnetic solid phase extraction coupled with desorption corona beam ionization-mass spectrometry for rapid analysis of antidepressants in human body fluids.

    PubMed

    Chen, Di; Zheng, Hao-Bo; Huang, Yun-Qing; Hu, Yu-Ning; Yu, Qiong-Wei; Yuan, Bi-Feng; Feng, Yu-Qi

    2015-08-21

    Ambient ionization techniques show good potential in rapid analysis of target compounds. However, a direct application of these ambient ionization techniques for the determination of analytes in a complex matrix is difficult due to the matrix interference and ion suppression. To resolve this problem, here we developed a strategy by coupling magnetic solid phase extraction (MSPE) with desorption corona beam ionization (DCBI)-mass spectrometry (MS). As a proof of concept, the pyrrole-coated Fe3O4 magnetic nanoparticles (Fe3O4@Ppy) were prepared and used for the extraction of antidepressants. After extraction, the Fe3O4@Ppy with trapped antidepressants was then directly subjected to DCBI-MS analysis with the aid of a homemade magnetic glass capillary. As the MSPE process is rapid and the direct DCBI-MS analysis does not need solvent desorption or chromatographic separation processes, the overall analysis can be completed within 3 min. The proposed MSPE-DCBI-MS method was then successfully used to determine antidepressants in human urine and plasma. The calibration curves were obtained in the range of 0.005-0.5 μg mL(-1) for urine and 0.02-1 μg mL(-1) for plasma with reasonable linearity (R(2) > 0.951). The limits of detection of three antidepressants were in the range of 0.2-1 ng mL(-1) for urine and 2-5 ng mL(-1) for plasma. Acceptable reproducibility for rapid analysis was achieved with relative standard deviations less than 19.1% and the relative recoveries were 85.2-118.7%. Taken together, the developed MSPE-DCBI-MS strategy offers a powerful capacity for rapid analysis of target compounds in a complex matrix, which would greatly expand the applications of ambient ionization techniques with plentiful magnetic sorbents. PMID:26145704

  3. Magnetic solid phase extraction coupled with desorption corona beam ionization-mass spectrometry for rapid analysis of antidepressants in human body fluids.

    PubMed

    Chen, Di; Zheng, Hao-Bo; Huang, Yun-Qing; Hu, Yu-Ning; Yu, Qiong-Wei; Yuan, Bi-Feng; Feng, Yu-Qi

    2015-08-21

    Ambient ionization techniques show good potential in rapid analysis of target compounds. However, a direct application of these ambient ionization techniques for the determination of analytes in a complex matrix is difficult due to the matrix interference and ion suppression. To resolve this problem, here we developed a strategy by coupling magnetic solid phase extraction (MSPE) with desorption corona beam ionization (DCBI)-mass spectrometry (MS). As a proof of concept, the pyrrole-coated Fe3O4 magnetic nanoparticles (Fe3O4@Ppy) were prepared and used for the extraction of antidepressants. After extraction, the Fe3O4@Ppy with trapped antidepressants was then directly subjected to DCBI-MS analysis with the aid of a homemade magnetic glass capillary. As the MSPE process is rapid and the direct DCBI-MS analysis does not need solvent desorption or chromatographic separation processes, the overall analysis can be completed within 3 min. The proposed MSPE-DCBI-MS method was then successfully used to determine antidepressants in human urine and plasma. The calibration curves were obtained in the range of 0.005-0.5 μg mL(-1) for urine and 0.02-1 μg mL(-1) for plasma with reasonable linearity (R(2) > 0.951). The limits of detection of three antidepressants were in the range of 0.2-1 ng mL(-1) for urine and 2-5 ng mL(-1) for plasma. Acceptable reproducibility for rapid analysis was achieved with relative standard deviations less than 19.1% and the relative recoveries were 85.2-118.7%. Taken together, the developed MSPE-DCBI-MS strategy offers a powerful capacity for rapid analysis of target compounds in a complex matrix, which would greatly expand the applications of ambient ionization techniques with plentiful magnetic sorbents.

  4. [The approbation of technique of mass spectrometry with matrix-activated laser desorption/ionization for identification of plague agent].

    PubMed

    Afanas'ev, M V; Ostiak, A S; Balakhonov, S V

    2014-08-01

    The study of sampling of strains of Y. pestis of main and altaic subspecies was implemented. The modern technique of identification of microorganisms was applied using MALDI-TOF mass spectrometry analysis. The evaluation of biological safety of method of sampling preparation was implemented. To supplement the identification base "BioTyper" the spectrum of typical strains of Y. pestis were obtained. The enhanced identification base was used to evaluate possibilities of application of MALDI-TOF technology for identification and taxonomic differentiation of Y. pestis from other representatives of genus of Yersinia. In the process of study a complete concordance of results of mass spectrometry identification and classic cultural method was observed. On the basis of mass spectrometry characteristic of analyzed sampling the differentiation between strains of Y. pestis of subspecies pestis and strains of subspecies altaica was implemented. The study results testify the effectiveness of application of mass spectrometry analysis for reliable interspecies and intraspecific differentiation of plague agent. The simplicity and velocity of sampling preparation and implementation of analysis and low cost of active storage allow considering the MALDI-TOF technology of mass spectrometry identification as highly perspective method for laboratory diagnostic of plague agent.

  5. Characterization of low-molecular weight iodine-terminated polyethylenes by gas chromatography/mass spectrometry and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with the use of derivatization.

    PubMed

    Zaikin, Vladimir G; Borisov, Roman S; Polovkov, Nikolai Yu; Zhilyaev, Dmitry I; Vinogradov, Aleksei A; Ivanyuk, Aleksei V

    2013-01-01

    Gas chromatography/mass spectrometry (GC/MS) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry, in conjunction with various derivatization approaches, have been applied to structure determination of individual oligomers and molecular-mass distributions (MMD) in low-molecular mass polyethylene having an iodine terminus. Direct GC/MS analysis has shown that the samples under investigation composed of polyethyelene-iodides (major components) and n-alkanes. Exchange reaction with methanol in the presence of NaOH gave rise to methoxy-derivatives and n-alkenes. Electron ionization mass spectra have shown that the former contained terminal methoxy groups indicating the terminal position of the iodine atom in the initial oligomers. MMD parameters have been determined with the aid of MALDI mass spectrometry followed by preliminary derivatization-formation of covalently bonded charge through the reaction of iodides with triphenylphosphine, trialkylamines, pyridine or quinoline. The mass spectra revealed well-resolved peaks for cationic parts of derivatized oligomers allowing the determination of MMD. The latter values have been compared with those calculated from GC/MS data.

  6. Evaluation of automated stir bar sorptive extraction-thermal desorption-gas chromatography electron capture negative ion mass spectrometry for the analysis of PBDEs and PBBs in sheep and human serum.

    PubMed

    Loconto, Paul R

    2009-09-01

    Stir-bar sorptive extraction and automated thermal desorption/cryotrapping interfaced to capillary gas chromatography and electron capture negative ion mass spectrometry is shown to effectively isolate and recover polybrominated diphenyl ethers and polybrominated biphenyls from sheep and human serum. This paper describes the development of the method and demonstrates the feasibility of using Twister with spiked serum. Conditions for conducting stir-bar sorptive extraction and for automated thermal desorption that led to acceptable analyte recoveries were optimized. The approach to sample preparation introduced here significantly reduces tedious labor and solvent consumption associated with conventional liquid-liquid extraction. PMID:19772742

  7. Matrix assisted laser desorption ionization time-of-flight mass spectrometry: Velocity measurements using orthogonal and axial injection and applications to characterization of wheat proteins

    NASA Astrophysics Data System (ADS)

    Dworschak, Ragnar G.

    velocities of matrix and analyte ions for more normal laser incidence, and for single crystals parallel to the sample surface compared to polycrystalline surfaces, suggesting the orientation of the crystal face with respect to the incident laser direction plays a role in the desorption process. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI/MS) was used to analyse the protein composition in several common and durum wheat varieties. Mass spectra were obtained directly from crude and partially purified wheat gliadin and reduced glutenin subunit fractions. Mass spectra of the gliadins and the low molecular weight glutenin subunits show a complex pattern of proteins in the 30--40 kDa range. The observed gliadin patterns showed some promise for variety identification. The mass spectra of the high molecular weight glutenin subunits are much simpler and the complete high molecular weight subunit profile can be determined directly from a single mass spectrum. This may prove particularly useful in wheat breeding programs for rapid identification of lines containing subunits associated with superior quality.

  8. A statistical methodology for the comparison of blue gel pen inks analyzed by laser desorption/ionization mass spectrometry.

    PubMed

    Weyermann, Céline; Bucher, Lukas; Majcherczyk, Paul

    2011-09-01

    A statistical methodology for the objective comparison of LDI-MS mass spectra of blue gel pen inks was evaluated. Thirty-three blue gel pen inks previously studied by RAMAN were analyzed directly on the paper using both positive and negative mode. The obtained mass spectra were first compared using relative areas of selected peaks using the Pearson correlation coefficient and the Euclidean distance. Intra-variability among results from one ink and inter-variability between results from different inks were compared in order to choose a differentiation threshold minimizing the rate of false negative (i.e. avoiding false differentiation of the inks). This yielded a discriminating power of up to 77% for analysis made in the negative mode. The whole mass spectra were then compared using the same methodology, allowing for a better DP in the negative mode of 92% using the Pearson correlation on standardized data. The positive mode results generally yielded a lower differential power (DP) than the negative mode due to a higher intra-variability compared to the inter-variability in the mass spectra of the ink samples. PMID:21889108

  9. Discrimination of different species from the genus Drosophila by intact protein profiling using matrix-assisted laser desorption ionization mass spectrometry

    PubMed Central

    2010-01-01

    Background The use of molecular biology-based methods for species identification and establishing phylogenetic relationships has supplanted traditional methods relying on morphological characteristics. While PCR-based methods are now the commonly accepted gold standards for these types of analysis, relatively high costs, time-consuming assay development or the need for a priori information about species-specific sequences constitute major limitations. In the present study, we explored the possibility to differentiate between 13 different species from the genus Drosophila via a molecular proteomic approach. Results After establishing a simple protein extraction procedure and performing matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) with intact proteins and peptides, we could show that most of the species investigated reproducibly yielded mass spectra that were adequate for species classification. Furthermore, a dendrogram generated by cluster analysis of total protein patterns agrees reasonably well with established phylogenetic relationships. Conclusion Considering the intra- and interspecies similarities and differences between spectra obtained for specimens of closely related Drosophila species, we estimate that species typing of insects and possibly other multicellular organisms by intact protein profiling (IPP) can be established successfully for species that diverged from a common ancestor about 3 million years ago. PMID:20374617

  10. Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray-Desorption Electrospray Ionization High-Resolution Mass Spectrometry

    SciTech Connect

    Tao, Shikang; Lu, Xiaohui; Levac, Nicole; Bateman, Adam P.; Nguyen, Tran B.; Bones, David L.; Nizkorodov, Sergey A.; Laskin, Julia; Laskin, Alexander; Yang, Xin

    2014-09-16

    Aerosol samples collected in the urban areas of Shanghai and Los Angeles were analyzed by nanospray-desorption electrospray ionization mass spectrometry (nano-DESI MS) with high mass resolution (m/Δm=100,000). Solvent mixtures of acetonitrile/water and acetonitrile/toluene were used to extract and ionize polar and non-polar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. Majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates in the two samples have distinctly different molecular characteristics. Specifically, organosulfates in the Los Angeles sample were dominated by isoprene- or monoterpene-derived products, while organosulfates of yet unknown origin in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degree of oxidation and unsaturation. The use of acetonitrile/toluene solvent facilitated identification of this type of organosulfates, suggesting they could be missed in previous studies relying on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the organosulfates detected in the Shanghai sample suggest that they may act as surfactants, and plausibly affect the surface tension and hygroscopicity of the atmospheric particulate matter. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in liquid phase could be the formation pathway of these special organosulfates. Finally, long-chain alkanes from vehicle emissions might be their precursors.

  11. Disposable polymeric high-density nanovial arrays for matrix assisted laser desorption/ionization-time of flight-mass spectrometry: I. Microstructure development and manufacturing.

    PubMed

    Marko-Varga, G; Ekstrom, S; Heildin, G; Nilsson, J; Laureli, T

    2001-10-01

    In order to meet the expected enormous demand for mass spectrometry (MS) throughput as a result of the current efforts to completely map the human proteome, this paper presents a new concept for low-cost high-throughput protein identification by matrix assisted laser desorption/ionization-time of flight-(MALDI-TOF)-MS peptide mapping using disposable polymeric high-density nanovial MALDI target plates. By means of microfabrication technology precision engineered nanovial arrays are fabricated in polymer substrates such as polymethylmethacrylate (PMMA) and polycarbonate (PC). The target plate fabrication processes investigated were precision micromilling, cold embossing and injection moulding (work in progress). Nanovial dimensions were 300, 400 or 500 microm. Typical array densities were 165 nanovials/cm2, which corresponds to 3,300 vials on a full Applied Biosystems MALDI target plate. Obtained MALDI data displayed equal mass resolution, accuracy, signal intensity for peptide standards as compared to high-density silicon nanovial arrays previously reported by our group [7], as well as conventional stainless steel or gold targets. PMID:11700729

  12. Acetone-activated polyimide electrospun nanofiber membrane for thin-film microextraction and thermal desorption-gas chromatography-mass spectrometric analysis of phenols in environmental water.

    PubMed

    Li, Shenghong; Wu, Dapeng; Yan, Xiaohui; Guan, Yafeng

    2015-09-11

    In this work, a polyimide nanofiber membrane was electrospun and applied as sorbent for thin film microextraction (TFME). After TFME of phenols in water samples, direct thermal desorption of the sorbent at 300°C followed by gas chromatography-mass spectrometric (TD-GC-MS) analysis was carried out. The extraction efficiency of TFME was enhanced by 6-12 times for phenols after activation with acetone. The positive effect of acetone activation was correlated to the increased hydrophilicity of the membrane. Extraction parameters, including mass of nanofiber membrane, pH value, NaCl concentration and extraction time, were optimized. Under optimal conditions, the LODs and LOQs for analysis of phenols in spiked purified water were 0.0006-0.008 and 0.002-0.025μgL(-1), respectively. The linearity range was more than two orders of magnitude (R>0.99). The RSDs of intra-batch and inter-batch were 4.3-7.4% and 2.7-10.6% (n=3). Finally the method was applied to real samples, including tap water, sea water, and waste water. These results indicate that the polyimide nanofiber membrane is a promising candidate as TFME sorbent for determination of polar analytes in water samples coupled with TD-GC-MS.

  13. Independent assessment of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) sample preparation quality: A novel statistical approach for quality scoring.

    PubMed

    Kooijman, Pieter C; Kok, Sander J; Weusten, Jos J A M; Honing, Maarten

    2016-05-01

    Preparation of samples according to an optimized method is crucial for accurate determination of polymer sample characteristics by Matrix-Assisted Laser Desorption Ionization (MALDI) analysis. Sample preparation conditions such as matrix choice, cationization agent, deposition technique or even the deposition volume should be chosen to suit the sample of interest. Many sample preparation protocols have been developed and employed, yet finding the optimal sample preparation protocol remains a challenge. Because an objective comparison between the results of diverse protocols is not possible, "gut-feeling" or "good enough" is often decisive in the search for an optimum. This implies that sub-optimal protocols are used, leading to a loss of mass spectral information quality. To address this problem a novel analytical strategy based on MALDI imaging and statistical data processing was developed in which eight parameters were formulated to objectively quantify the quality of sample deposition and optimal MALDI matrix composition and finally sum up to an overall quality score of the sample deposition. These parameters can be established in a fully automated way using commercially available mass spectrometry imaging instruments without any hardware adjustments. With the newly developed analytical strategy the highest quality MALDI spots were selected, resulting in more reproducible and more valuable spectra for PEG in a variety of matrices. Moreover, our method enables an objective comparison of sample preparation protocols for any analyte and opens up new fields of investigation by presenting MALDI performance data in a clear and concise way.

  14. Evaluation of the Andromas Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry System for Identification of Aerobically Growing Gram-Positive Bacilli

    PubMed Central

    Farfour, E.; Leto, J.; Barritault, M.; Barberis, C.; Meyer, J.; Dauphin, B.; Le Guern, A.-S.; Leflèche, A.; Badell, E.; Guiso, N.; Leclercq, A.; Le Monnier, A.; Lecuit, M.; Rodriguez-Nava, V.; Bergeron, E.; Raymond, J.; Vimont, S.; Bille, E.; Carbonnelle, E.; Guet-Revillet, H.; Lécuyer, H.; Beretti, J.-L.; Vay, C.; Berche, P.; Ferroni, A.; Nassif, X.

    2012-01-01

    Matrix-associated laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) is a rapid and simple microbial identification method. Previous reports using the Biotyper system suggested that this technique requires a preliminary extraction step to identify Gram-positive rods (GPRs), a technical issue that may limit the routine use of this technique to identify pathogenic GPRs in the clinical setting. We tested the accuracy of the MALDI-TOF MS Andromas strategy to identify a set of 659 GPR isolates representing 16 bacterial genera and 72 species by the direct colony method. This bacterial collection included 40 C. diphtheriae, 13 C. pseudotuberculosis, 19 C. ulcerans, and 270 other Corynebacterium isolates, 32 L. monocytogenes and 24 other Listeria isolates, 46 Nocardia, 75 Actinomyces, 18 Actinobaculum, 11 Propionibacterium acnes, 18 Propionibacterium avidum, 30 Lactobacillus, 21 Bacillus, 2 Rhodococcus equi, 2 Erysipelothrix rhusiopathiae, and 38 other GPR isolates, all identified by reference techniques. Totals of 98.5% and 1.2% of non-Listeria GPR isolates were identified to the species or genus level, respectively. Except for L. grayi isolates that were identified to the species level, all other Listeria isolates were identified to the genus level because of highly similar spectra. These data demonstrate that rapid identification of pathogenic GPRs can be obtained without an extraction step by MALDI-TOF mass spectrometry. PMID:22692743

  15. Reversed phase liquid chromatography hyphenated to continuous flow-extractive desorption electrospray ionization-mass spectrometry for analysis and charge state manipulation of undigested proteins.

    PubMed

    Li, Li; Yang, Samuel H; Vidova, Veronika; Rice, Elisa M; Wijeratne, Aruna B; Havlíček, Vladimír; Schug, Kevin A

    2015-01-01

    The application of continuous flow-extractive desorption electrospray ionization (CF-EDESI), an ambient ionization source demonstrated previously for use with intact protein analysis, is expanded here for the coupling of reversed phase protein separations to mass spectrometry. This configuration allows the introduction of charging additives to enhance detection without affecting the chromatographic separation mechanism. Two demonstrations of the advantages of CF-EDESI are presented in this work. First, a proof-of- principle is presented to demonstrate the applicability of hyphenation of liquid chromatography (LC) to CF- EDESI. LC-CF-EDESI-MS has good sensitivity compared to LC-electrospray ionization (ESI)-mass spectrometry. Second, the supercharging mechanism investigated in CF-EDESI provides an insight into a highly debated supercharging process in ESI. The results indicate that the mechanism of protein charging seen in HPLC-CF-EDESI is different from supercharging phenomena in conventional ESI. The surface tension mechanism and binding mechanism may both contribute to protein supercharging in ESI. PMID:26307717

  16. Biomarkers probed in saliva by surface plasmon resonance imaging coupled to matrix-assisted laser desorption/ionization mass spectrometry in array format.

    PubMed

    Musso, Johana; Buchmann, William; Gonnet, Florence; Jarroux, Nathalie; Bellon, Sophie; Frydman, Chiraz; Brunet, Didier-Luc; Daniel, Regis

    2015-02-01

    Detection of protein biomarkers is of major interest in proteomics. This work reports the analysis of protein biomarkers directly from a biological fluid, human saliva, by surface plasmon resonance imaging coupled to mass spectrometry (SPRi-MS), using a functionalized biochip in an array format enabling multiplex SPR-MS analysis. The SPR biochip presented a gold surface functionalized by a self-assembled monolayer of short poly(ethylene oxide) chains carrying an N-hydroxysuccinimide end-group for the immobilization of antibodies. The experiments were accomplished without any sample pre-purification or spiking with the targeted biomarkers. SPRi monitoring of the interactions, immune capture from the biochip surface, and finally on-chip matrix-assisted laser desorption/ionization-MS structural identification of two protein biomarkers, salivary α-amylase and lysozyme, were successively achieved directly from saliva at the femtomole level. For lysozyme, the on-chip MS identification was completed by a proteomic analysis based on an on-chip proteolysis procedure and a peptide mass fingerprint. PMID:25524230

  17. Quantitative analysis of poly- and perfluoroalkyl compounds in water matrices using high resolution mass spectrometry: optimization for a laser diode thermal desorption method.

    PubMed

    Munoz, Gabriel; Vo Duy, Sung; Budzinski, Hélène; Labadie, Pierre; Liu, Jinxia; Sauvé, Sébastien

    2015-06-30

    An alternative analysis technique for the quantitation of 15 poly- and perfluoroalkyl substances (PFASs) in water matrices is reported. Analysis time between each sample was reduced to less than 20s, all target molecules being analyzed in a single run with the use of laser diode thermal desorption atmospheric pressure chemical ionization (LDTD/APCI) coupled with high resolution accurate mass (HRMS) orbitrap mass spectrometry. LDTD optimal settings were investigated using either one-factor-at-a-time or experimental design methodologies, while orbitrap parameters were optimized simultaneously by means of a Box-Behnken design. Following selection of an adequate sample concentration and purification procedure based on solid-phase extraction and graphite clean-up, the method was validated in an influent wastewater matrix. Environmentally significant limits of detection were reported (0.3-4ngL(-1) in wastewater and 0.03-0.2ngL(-1) in surface water) and out of the 15 target analytes, 11 showed excellent accuracies (±20% of the target values) and recovery rates (75-125%). The method was successfully applied to a selection of environmental samples, including wastewater samples in 7 locations across Canada, as well as surface and tap water samples from the Montreal region, providing insights into the degree of PFAS contamination in this area. PMID:26041525

  18. Matrix-assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS) Can Precisely Discriminate the Lineages of Listeria monocytogenes and Species of Listeria.

    PubMed

    Ojima-Kato, Teruyo; Yamamoto, Naomi; Takahashi, Hajime; Tamura, Hiroto

    2016-01-01

    The genetic lineages of Listeria monocytogenes and other species of the genus Listeria are correlated with pathogenesis in humans. Although matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) has become a prevailing tool for rapid and reliable microbial identification, the precise discrimination of Listeria species and lineages remains a crucial issue in clinical settings and for food safety. In this study, we constructed an accurate and reliable MS database to discriminate the lineages of L. monocytogenes and the species of Listeria (L. monocytogenes, L. innocua, L. welshimeri, L. seeligeri, L. ivanovii, L. grayi, and L. rocourtiae) based on the S10-spc-alpha operon gene encoded ribosomal protein mass spectrum (S10-GERMS) proteotyping method, which relies on both genetic information (genomics) and observed MS peaks in MALDI-TOF MS (proteomics). The specific set of eight biomarkers (ribosomal proteins L24, L6, L18, L15, S11, S9, L31 type B, and S16) yielded characteristic MS patterns for the lineages of L. monocytogenes and the different species of Listeria, and led to the construction of a MS database that was successful in discriminating between these organisms in MALDI-TOF MS fingerprinting analysis followed by advanced proteotyping software Strain Solution analysis. We also confirmed the constructed database on the proteotyping software Strain Solution by using 23 Listeria strains collected from natural sources.

  19. Determination of off-flavor compounds, 2-methylisoborneol and geosmin, in salmon fillets using stir bar sorptive extraction-thermal desorption coupled with gas chromatography-mass spectrometry.

    PubMed

    Ruan, E D; Aalhus, J L; Summerfelt, S T; Davidson, J; Swift, B; Juárez, M

    2013-12-20

    A sensitive and solvent-less method for the determination of musty and earthy off-flavor compounds, 2-methylisoborneol (MIB) and geosmin (GSM), in salmon tissue was developed using stir bar sorptive extraction-thermal desorption coupled with gas chromatography-mass spectrometry (SBSE-TD-GCMS). MIB and GSM were solid phase extracted using polydimethylsiloxane (PDMS) coated stir bars, analyzed by gas chromatography, and detected in full scan mode of mass selective detector (MSD). Using this method, the calibration curves of MIB and GSM were linear in the range of 0.3-100ng/L, with a correlation coefficient above 0.999 and RSDs less than 4% (n=4). The limit of detection (LOD, S/N=3, n=6) and limit of quantification (LOQ, S/N=10, n=6) of MIB and GSM were both ∼0.3 and 1ng/L, respectively. The recoveries of MIB and GSM were 22% and 29% by spike in 30ng/L standard compounds, 23% and 30% by spike-in 100ng/L standard compounds in salmon tissue samples with good precision (<8% of RSDs, n=6), respectively. The recoveries of MIB and GSM were better than reported methodologies using SPME fibres (<10%) in fish tissue samples. This method was successfully applied to monitor and characterize depurated salmon fillet samples (0, 3, 6 and 10 days).

  20. Method for Detection and Quantitation of Fathead Minnow Vitellogenin (Vtg) by Liquid Chromatography and Matrix Assisted Laser Desorption/ Ionization Mass Spectrometry

    SciTech Connect

    Wunschel, David S.; Schultz, Irv R.; Skillman, Ann D.; Wahl, Karen L.

    2005-03-11

    Vitellogenin (Vtg) is a well recognized biomarker of estrogen exposure in many species, particularly fish. This large protein shares a high degree of sequence homology across a large number of species. Quantitative measurement is currently done using antibody-based assays. These assays frequently require purification of Vtg and antibody production from each species because there is poor cross reactivity between antibodies for different fish. Therefore, complementary methods of measuring Vtg are desirable. Mass spectrometric (MS) analysis coupled to database searching offers the promise of a general method for protein identification. In this study we used the well characterized Vtg from rainbow trout (O. mykiss) to evaluate the analytical parameters for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) analysis of the intact and tryptic digested protein. An analytical scale HPLC separation combined with MALDI-MS was used to measure and confirm the identity of Vtg from the plasma of an important species for regulatory agencies, fathead minnow (Pimephales promelas). The small volume requirement of this method (< 10 uL) was found to be compatible with the plasma volume obtained from a few minnows. A semi quantitative measurement of Vtg from minnows exposed to estradiol was achieved, which was similar to previously obtained ELISA data.

  1. Matrix-assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS) Can Precisely Discriminate the Lineages of Listeria monocytogenes and Species of Listeria

    PubMed Central

    Yamamoto, Naomi; Takahashi, Hajime; Tamura, Hiroto

    2016-01-01

    The genetic lineages of Listeria monocytogenes and other species of the genus Listeria are correlated with pathogenesis in humans. Although matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) has become a prevailing tool for rapid and reliable microbial identification, the precise discrimination of Listeria species and lineages remains a crucial issue in clinical settings and for food safety. In this study, we constructed an accurate and reliable MS database to discriminate the lineages of L. monocytogenes and the species of Listeria (L. monocytogenes, L. innocua, L. welshimeri, L. seeligeri, L. ivanovii, L. grayi, and L. rocourtiae) based on the S10-spc-alpha operon gene encoded ribosomal protein mass spectrum (S10-GERMS) proteotyping method, which relies on both genetic information (genomics) and observed MS peaks in MALDI-TOF MS (proteomics). The specific set of eight biomarkers (ribosomal proteins L24, L6, L18, L15, S11, S9, L31 type B, and S16) yielded characteristic MS patterns for the lineages of L. monocytogenes and the different species of Listeria, and led to the construction of a MS database that was successful in discriminating between these organisms in MALDI-TOF MS fingerprinting analysis followed by advanced proteotyping software Strain Solution analysis. We also confirmed the constructed database on the proteotyping software Strain Solution by using 23 Listeria strains collected from natural sources. PMID:27442502

  2. Matrix-assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS) Can Precisely Discriminate the Lineages of Listeria monocytogenes and Species of Listeria.

    PubMed

    Ojima-Kato, Teruyo; Yamamoto, Naomi; Takahashi, Hajime; Tamura, Hiroto

    2016-01-01

    The genetic lineages of Listeria monocytogenes and other species of the genus Listeria are correlated with pathogenesis in humans. Although matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) has become a prevailing tool for rapid and reliable microbial identification, the precise discrimination of Listeria species and lineages remains a crucial issue in clinical settings and for food safety. In this study, we constructed an accurate and reliable MS database to discriminate the lineages of L. monocytogenes and the species of Listeria (L. monocytogenes, L. innocua, L. welshimeri, L. seeligeri, L. ivanovii, L. grayi, and L. rocourtiae) based on the S10-spc-alpha operon gene encoded ribosomal protein mass spectrum (S10-GERMS) proteotyping method, which relies on both genetic information (genomics) and observed MS peaks in MALDI-TOF MS (proteomics). The specific set of eight biomarkers (ribosomal proteins L24, L6, L18, L15, S11, S9, L31 type B, and S16) yielded characteristic MS patterns for the lineages of L. monocytogenes and the different species of Listeria, and led to the construction of a MS database that was successful in discriminating between these organisms in MALDI-TOF MS fingerprinting analysis followed by advanced proteotyping software Strain Solution analysis. We also confirmed the constructed database on the proteotyping software Strain Solution by using 23 Listeria strains collected from natural sources. PMID:27442502

  3. Identification of medically relevant species of arthroconidial yeasts by use of matrix-assisted laser desorption ionization-time of flight mass spectrometry.

    PubMed

    Kolecka, Anna; Khayhan, Kantarawee; Groenewald, Marizeth; Theelen, Bart; Arabatzis, Michael; Velegraki, Aristea; Kostrzewa, Markus; Mares, Mihai; Taj-Aldeen, Saad J; Boekhout, Teun

    2013-08-01

    Matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) was used for an extensive identification study of arthroconidial yeasts, using 85 reference strains from the CBS-KNAW yeast collection and 134 clinical isolates collected from medical centers in Qatar, Greece, and Romania. The test set included 72 strains of ascomycetous yeasts (Galactomyces, Geotrichum, Saprochaete, and Magnusiomyces spp.) and 147 strains of basidiomycetous yeasts (Trichosporon and Guehomyces spp.). With minimal preparation time, MALDI-TOF MS proved to be an excellent diagnostic tool that provided reliable identification of most (98%) of the tested strains to the species level, with good discriminatory power. The majority of strains were correctly identified at the species level with good scores (>2.0) and seven of the tested strains with log score values between 1.7 and 2.0. The MALDI-TOF MS results obtained were consistent with validated internal transcribed spacer (ITS) and/or large subunit (LSU) ribosomal DNA sequencing results. Expanding the mass spectrum database by increasing the number of reference strains for closely related species, including those of nonclinical origin, should enhance the usefulness of MALDI-TOF MS-based diagnostic analysis of these arthroconidial fungi in medical and other laboratories.

  4. Quantitation of lysergic acid diethylamide in urine using atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry.

    PubMed

    Cui, Meng; McCooeye, Margaret A; Fraser, Catharine; Mester, Zoltán

    2004-12-01

    A quantitative method was developed for analysis of lysergic acid diethylamide (LSD) in urine using atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry (AP MALDI-ITMS). Following solid-phase extraction of LSD from urine samples, extracts were analyzed by AP MALDI-ITMS. The identity of LSD was confirmed by fragmentation of the [M + H](+) ion using tandem mass spectrometry. The quantification of LSD was achieved using stable-isotope-labeled LSD (LSD-d(3)) as the internal standard. The [M + H](+) ion fragmented to produce a dominant fragment ion, which was used for a selected reaction monitoring (SRM) method for quantitative analysis of LSD. SRM was compared with selected ion monitoring and produced a wider linear range and lower limit of quantification. For SRM analysis of samples of LSD spiked in urine, the calibration curve was linear in the range of 1-100 ng/mL with a coefficient of determination, r(2), of 0.9917. This assay was used to determine LSD in urine samples and the AP MALDI-MS results were comparable to the HPLC/ ESI-MS results.

  5. Detection of bacteria from biological mixtures using immunomagnetic separation combined with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

    USGS Publications Warehouse

    Madonna, A.J.; Basile, F.; Furlong, E.; Voorhees, K.J.

    2001-01-01

    A rapid method for identifying specific bacteria from complex biological mixtures using immunomagnetic separation coupled to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry has been developed. The technique employs commercially available magnetic beads coated with polycolonal antibodies raised against specific bacteria and whole cell analysis by MALDI-MS. A suspension of a bacterial mixture is mixed with the immunomagnetic beads specific for the target microorganism. After a short incubation period (20 mins) the bacteria captured by the beads are washed, resuspended in deionized H2O and directly applied onto a MALDI probe. Liquid suspensions containing bacterial mixtures can be screened within 1 h total analysis time. Positive tests result in the production of a fingerprint mass spectrum primarily consisting of protein biomarkers characteristic of the targeted microorganism. Using this procedure, Salmonella choleraesuis was isolated and detected from standard bacterial mixtures and spiked samples of river water, human urine, and chicken blood. Copyright ?? 2001 John Wiley & Sons, Ltd.

  6. Localization of ginsenosides in Panax ginseng with different age by matrix-assisted laser-desorption/ionization time-of-flight mass spectrometry imaging.

    PubMed

    Bai, Hangrui; Wang, Shujuan; Liu, Jianjun; Gao, Dan; Jiang, Yuyang; Liu, Hongxia; Cai, Zongwei

    2016-07-15

    The root of Panax ginseng C.A. Mey. (P. ginseng) is one of the most popular traditional Chinese medicines, with ginsenosides as its main bioactive components. Because different ginsenosides have varied pharmacological effects, extraction and separation of ginsenosides are usually required for the investigation of pharmacological effects of different ginsenosides. However, the contents of ginsenosides vary with the ages and tissues of P. ginseng root. In this research, an efficient method to explore the distribution of ginsenosides and differentiate P. ginseng roots with different ages was developed based on matrix assisted laser desorption/ionization time-of-flight mass spectrometry imaging (MALDI-TOF-MSI). After a simple sample preparation, there were 18 peaks corresponding to 31 ginsenosides with distinct localization in the mass range of m/z 700-1400 identified by MALDI-TOF-MSI and MALDI-TOF-MS/MS. All the three types of ginsenosides were successfully detected and visualized in images, which could be correlated with anatomical features. The P. ginseng at the ages of 2, 4 and 6 could be differentiated finely through the principal component analysis of data collected from the cork based on the ion images but not data from the whole tissue. The experimental result implies that the established method for the direct analysis of metabolites in plant tissues has high potential for the rapid identification of metabolites and analysis of their localizations in medicinal herbs. Furthermore, this technique also provides valuable information for the component-specific extraction and pharmacological research of herbs.

  7. Identification of adulteration in water buffalo mozzarella and in ewe cheese by using whey proteins as biomarkers and matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Cozzolino, R; Passalacqua, S; Salemi, S; Garozzo, D

    2002-09-01

    A rapid and accurate method to identify bovine and ewe milk adulteration of fresh water buffalo mozzarella cheese by using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) is described. The differentiation among mozzarella made from water buffalo milk and from mixtures of less expensive bovine and, more recently, ewe milk with water buffalo milk is achieved using whey proteins, alpha-lactalbumin and beta-lactoglobulins as molecular markers. It is worth noting that the method proposed here is, to our knowledge, the first strategy able to characterize possible fraudulent additions of ewe milk in samples of water buffalo milk devoted to the production of water buffalo mozzarella cheese. In addition, a linear relationship was found between the relative response of the molecular ion and the abundance of the analysed whey proteins. This demonstrates that this approach can be used to determine the amount of bovine or ovine milk added to water buffalo milk employed for mozzarella cheese production. Furthermore, this method also appears suitable for the analysis of ewe cheese. Hence these findings open the way to a new field for mass spectrometry in the evaluation of possible fraudulence in dairy industry production.

  8. The value of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry in identifying clinically relevant bacteria: a comparison with automated microbiology system

    PubMed Central

    Zhou, Chunmei; Huang, Shenglei; Shan, Yuzhang; Ye, Xiangru

    2014-01-01

    Background Matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) has been developed as a new-type soft ionization mass spectrometry in the recent year. Increasing number of clinical microbiological laboratories consider it as an innovate approach for bacterial identification. Methods A total of 876 clinical strains, comprising 52 species in 27 genus, were obtained from Fudan University Affiliated Zhongshan Hospital. We compared the identification accuracy of the Vitek MS system (bioMerieux, Marcy l’Etoile) to other conventional methods for bacterial identification. 16S rRNA gene sequencing was performed as a reference identification method in cases of discrepant results. Results The Vitek MS system consistently produced accurate results within minutes of loading, while conventional methods required several hours to produce identification results. Among the 876 isolates, the overall performance of Vitek MS was significantly better than the conventional method both for correct species identification (830, 94.7% vs. 746, 85.2%, respectively, P=0.000). Conclusions Compared to traditional identification methods, MALDI-TOF MS is a rapid, accurate and economical technique to enhance the clinical value of microorganism identification. PMID:24822117

  9. Qualitative and quantitative DNA and RNA analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Ding, Chunming

    2006-01-01

    Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) gives extremely precise reading of mass-to-charge ratios (two analytes differ by 1 Da can be distinguished) and provides high sensitivity (less than 1 fmole of a DNA oligonucleotide can be detected), allowing DNA quantifications with single base specificity and single DNA molecule sensitivity (coupled with polymerase chain reaction [PCR]). To quantify a DNA sequence of interest, a competitive synthetic (60-80 bases) oligonucleotide standard with an artificial single base mutation in the middle is introduced, and these two virtually identical sequences are co-amplified by PCR. A third primer (extension primer) is designed to anneal to the region immediately upstream of the mutation site. Depending on the specific mutation introduced and the ddNTP/dNTP mixtures used, either one or two bases are added to the extension primer to produce two extension products from the two templates. Last, the two extension products are detected and quantified by high-throughput MALDI-TOF MS. In addition, with an improved primer extension method called single allele base extension reaction (SABER), rare mutant DNA can be robustly detected even when normal DNA is present at 50-fold or more than the DNA mutants.

  10. Global optimization of the infrared matrix-assisted laser desorption electrospray ionization (IR MALDESI) source for mass spectrometry using statistical design of experiments.

    PubMed

    Barry, Jeremy A; Muddiman, David C

    2011-12-15

    Design of experiments (DOE) is a systematic and cost-effective approach to system optimization by which the effects of multiple parameters and parameter interactions on a given response can be measured in few experiments. Herein, we describe the use of statistical DOE to improve a few of the analytical figures of merit of the infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) source for mass spectrometry. In a typical experiment, bovine cytochrome c was ionized via electrospray, and equine cytochrome c was desorbed and ionized by IR-MALDESI such that the ratio of equine:bovine was used as a measure of the ionization efficiency of IR-MALDESI. This response was used to rank the importance of seven source parameters including flow rate, laser fluence, laser repetition rate, ESI emitter to mass spectrometer inlet distance, sample stage height, sample plate voltage, and the sample to mass spectrometer inlet distance. A screening fractional factorial DOE was conducted to designate which of the seven parameters induced the greatest amount of change in the response. These important parameters (flow rate, stage height, sample to mass spectrometer inlet distance, and laser fluence) were then studied at higher resolution using a full factorial DOE to obtain the globally optimized combination of parameter settings. The optimum combination of settings was then compared with our previously determined settings to quantify the degree of improvement in detection limit. The limit of detection for the optimized conditions was approximately 10 attomoles compared with 100 femtomoles for the previous settings, which corresponds to a four orders of magnitude improvement in the detection limit of equine cytochrome c.

  11. Characterization of on-target generated tryptic peptides from Giberella zeae conidia spore proteins by means of matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Dong, Hongjuan; Marchetti-Deschmann, Martina; Allmaier, Günter

    2014-01-01

    Traditionally characterization of microbial proteins is performed by a complex sequence of steps with the final step to be either Edman sequencing or mass spectrometry, which generally takes several weeks or months to be complete. In this work, we proposed a strategy for the characterization of tryptic peptides derived from Giberella zeae (anamorph: Fusarium graminearum) proteins in parallel to intact cell mass spectrometry (ICMS) in which no complicated and time-consuming steps were needed. Experimentally, after a simple washing treatment of the spores, the aliquots of the intact G. zeae macro conidia spores solution, were deposited two times onto one MALDI (matrix-assisted laser desorption ionization) mass spectrometry (MS) target (two spots). One spot was used for ICMS and the second spot was subject to a brief on-target digestion with bead-immobilized or non-immobilized trypsin. Subsequently, one spot was analyzed immediately by MALDI MS in the linear mode (ICMS) whereas the second spot containing the digested material was investigated by MALDI MS in the reflectron mode ("peptide mass fingerprint") followed by protonated peptide selection for MS/MS (post source decay (PSD) fragment ion) analysis. Based on the formed fragment ions of selected tryptic peptides a complete or partial amino acid sequence was generated by manual de novo sequencing. These sequence data were used for homology search for protein identification. Finally four different peptides of varying abundances have been identified successfully allowing the verification that our desorbed/ionized surface compounds were indeed derived from proteins. The presence of three different proteins could be found unambiguously. Interestingly, one of these proteins is belonging to the ribosomal superfamily which indicates that not only surface-associated proteins were digested. This strategy minimized the amount of time and labor required for obtaining deeper information on spore preparations within the

  12. Identification of Enterobacteriaceae by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry using the VITEK MS system.

    PubMed

    Richter, S S; Sercia, L; Branda, J A; Burnham, C-A D; Bythrow, M; Ferraro, M J; Garner, O B; Ginocchio, C C; Jennemann, R; Lewinski, M A; Manji, R; Mochon, A B; Rychert, J A; Westblade, L F; Procop, G W

    2013-12-01

    This multicenter study evaluated the accuracy of matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry identifications from the VITEK MS system (bioMérieux, Marcy l'Etoile, France) for Enterobacteriaceae typically encountered in the clinical laboratory. Enterobacteriaceae isolates (n = 965) representing 17 genera and 40 species were analyzed on the VITEK MS system (database v2.0), in accordance with the manufacturer's instructions. Colony growth (≤72 h) was applied directly to the target slide. Matrix solution (α-cyano-4-hydroxycinnamic acid) was added and allowed to dry before mass spectrometry analysis. On the basis of the confidence level, the VITEK MS system provided a species, genus only, or no identification for each isolate. The accuracy of the mass spectrometric identification was compared to 16S rRNA gene sequencing performed at MIDI Labs (Newark, DE). Supplemental phenotypic testing was performed at bioMérieux when necessary. The VITEK MS result agreed with the reference method identification for 96.7% of the 965 isolates tested, with 83.8% correct to the species level and 12.8% limited to a genus-level identification. There was no identification for 1.7% of the isolates. The VITEK MS system misidentified 7 isolates (0.7 %) as different genera. Three Pantoea agglomerans isolates were misidentified as Enterobacter spp. and single isolates of Enterobacter cancerogenus, Escherichia hermannii, Hafnia alvei, and Raoultella ornithinolytica were misidentified as Klebsiella oxytoca, Citrobacter koseri, Obesumbacterium proteus, and Enterobacter aerogenes, respectively. Eight isolates (0.8 %) were misidentified as a different species in the correct genus. The VITEK MS system provides reliable mass spectrometric identifications for Enterobacteriaceae. PMID:23818163

  13. Attomole biomolecule mass analysis by matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance.

    PubMed

    Solouki, T; Marto, J A; White, F M; Guan, S; Marshall, A G

    1995-11-15

    Significantly improved sensitivity for analysis of biomolecules by MALDI FT-ICR mass spectrometry is achieved by (i) microscope-monitored sample deposition onto a small indentation on the probe tip and (ii) multiple remeasurement of ions from a single laser shot. A simple modification to the solids probe tip allows for microdeposition of a few amols of analyte onto small indentation spots previously aligned with the laser beam. Ion multiple remeasurement of the same ion packet enhances the signal-to-noise ratio and thus extends the achievable FT-ICR MS detection limit. We demonstrate that FT-ICR can be used to detect parent and structurally significant fragment ions of peptides and phospholipids at low amol amounts. Positive ion mass spectra for approximately 90 amol of a mixture of angiotensin II and bradykinin, approximately 40 amol of dipalmitoylglycerophosphatidylcholine, and approximately 8 amol of substance P constitute the lowest reported detection limits to date for FT-ICR mass analysis of MALDI-generated ions.

  14. Potential of laser ablation and laser desorption mass spectrometry to characterize organic and inorganic environmental pollutants on dust particles.

    PubMed

    Carré, Vincent; Aubriet, Frédéric; Scheepers, Paul T; Krier, Gabriel; Muller, Jean-François

    2005-01-01

    Stainless steel factories are known to release particles into the atmosphere. Such particulate matter contains significant amounts of heavy metals or toxic inorganic compounds and organic pollutants such as, for example, Cr(VI) and polycyclic aromatic hydrocarbons (PAHs). The investigation of Cr(VI) and PAHs is often complicated by the associated matrix. Organic and inorganic pollutants present in stainless steel dust particles have been investigated with the same laser microprobe mass spectrometer according to two original methodologies. These analytical methods do not require time-consuming pretreatment (extraction, solubilization) or preconcentration steps. More specifically, experiments are conducted with a Fourier transform ion cyclotron resonance mass spectrometer coupled to an ArF (193 nm) or a tripled frequency Nd-YAG (355 nm) laser. Experiments at 355 nm allow the nature of the most frequently occurring Cr(III)/Cr(VI) compounds in dust particles to be identified. Examination of PAHs at 193 nm is assisted by the formation of pi-complexes with 7,7',8,8'-tetracyanoquinodimethane to prevent their evaporation in the mass spectrometer during analysis and to ensure an increase in sensitivity.

  15. Ultra-Fast Laser Desorption/Laser Ionization Mass Spectrometry for the Organic Analysis of Stardust Sample Return

    NASA Technical Reports Server (NTRS)

    Clemett, Simon J.; McKay, David S.

    2005-01-01

    The STARDUST sample return capsule is anticipated to provide 500-1000 cometary particles 15 m in size. These were collected during the 340 km flyby of Comet P/Wild-2 and impacted the aerogel collection medium at a relative velocity of approx. 6.1 /kms. Hypervelocity impact studies suggest that some fraction of the original organic inventory of collected particles ought to remain intact, although there is likely to be a significant amount of devolatilization and disassociation of the lower mass organic fraction.

  16. Comparative study of matrices for their use in the rapid screening of anabolic steroids by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry.

    PubMed

    Galesio, M; Rial-Otero, R; Capelo-Martínez, J-L

    2009-06-01

    New data on sample preparation and matrix selection for the fast screening of androgenic anabolic steroids (AAS) by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) is presented. The rapid screening of 15 steroids included in the World Anti-Doping Agency (WADA) prohibited list using MALDI was evaluated. Nine organic and two inorganic matrices were assessed in order to determine the best matrix for steroid identification in terms of ionisation yield and interference by characteristic matrix ions. The best results were achieved for the organic matrices 2-(4-hydroxyphenylazo)benzoic acid (HABA) and trans-3-indoleacrylic acid (IAA). Good signals for all the steroids studied were obtained for concentrations as low as 0.010 and 0.050 microg/mL on the MALDI sample plate for the HABA and IAA matrices, respectively. For these two matrices, the sensitivity achieved by MALDI is comparable with the sensitivity achieved by gas chromatography/mass spectrometry (GC/MS), which is the conventional technique used for AAS detection. Furthermore, the accuracy and precision obtained with MALDI are very good, since an internal mass calibration is performed with the matrix ions. For the inorganic matrices, laser fluences higher than those used with organic matrices are required to obtain good MALDI signals. When inorganic matrices were used in combination with glycerol as a dispersing agent, an important reduction of the background noise was observed. Urine samples spiked with the study compounds were processed by solid-phase extraction (SPE) and the screening was consistently positive.

  17. Chemical analysis of pharmaceuticals and explosives in fingermarks using matrix-assisted laser desorption ionization/time-of-flight mass spectrometry.

    PubMed

    Kaplan-Sandquist, Kimberly; LeBeau, Marc A; Miller, Mark L

    2014-02-01

    Chemical analysis of latent fingermarks, "touch chemistry," has the potential of providing intelligence or forensically relevant information. Matrix-assisted laser desorption ionization/time-of-flight mass spectrometry (MALDI/TOF MS) was used as an analytical platform for obtaining mass spectra and chemical images of target drugs and explosives in fingermark residues following conventional fingerprint development methods and MALDI matrix processing. There were two main purposes of this research: (1) develop effective laboratory methods for detecting drugs and explosives in fingermark residues and (2) determine the feasibility of detecting drugs and explosives after casual contact with pills, powders, and residues. Further, synthetic latent print reference pads were evaluated as mimics of natural fingermark residue to determine if the pads could be used for method development and quality control. The results suggest that artificial amino acid and sebaceous oil residue pads are not suitable to adequately simulate natural fingermark chemistry for MALDI/TOF MS analysis. However, the pads were useful for designing experiments and setting instrumental parameters. Based on the natural fingermark residue experiments, handling whole or broken pills did not transfer sufficient quantities of drugs to allow for definitive detection. Transferring drugs or explosives in the form of powders and residues was successful for preparing analytes for detection after contact with fingers and deposition of fingermark residue. One downfall to handling powders was that the analyte particles were easily spread beyond the original fingermark during development. Analyte particles were confined in the original fingermark when using transfer residues. The MALDI/TOF MS was able to detect procaine, pseudoephedrine, TNT, and RDX from contact residue under laboratory conditions with the integration of conventional fingerprint development methods and MALDI matrix. MALDI/TOF MS is a nondestructive

  18. Identification of Haemophilus influenzae Type b Isolates by Use of Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry

    PubMed Central

    Månsson, Viktor; Kostrzewa, Markus; Nilson, Bo; Riesbeck, Kristian

    2015-01-01

    Haemophilus influenzae type b (Hib) is, in contrast to non-type b H. influenzae, associated with severe invasive disease, such as meningitis and epiglottitis, in small children. To date, accurate H. influenzae capsule typing requires PCR, a time-consuming and cumbersome method. Matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) provides rapid bacterial diagnostics and is increasingly used in clinical microbiology laboratories. Here, MALDI-TOF MS was evaluated as a novel approach to separate Hib from other H. influenzae. PCR-verified Hib and non-Hib reference isolates were selected based on genetic and spectral characteristics. Mass spectra of reference isolates were acquired and used to generate different classification algorithms for Hib/non-Hib differentiation using both ClinProTools and the MALDI Biotyper software. A test series of mass spectra from 33 Hib and 77 non-Hib isolates, all characterized by PCR, was used to evaluate the algorithms. Several algorithms yielded good results, but the two best were a ClinProTools model based on 22 separating peaks and subtyping main spectra (MSPs) using MALDI Biotyper. The ClinProTools model had a sensitivity of 100% and a specificity of 99%, and the results were 98% reproducible using a different MALDI-TOF MS instrument. The Biotyper subtyping MSPs had a sensitivity of 97%, a specificity of 100%, and 93% reproducibility. Our results suggest that it is possible to use MALDI-TOF MS to differentiate Hib from other H. influenzae. This is a promising method for rapidly identifying Hib in unvaccinated populations and for the screening and surveillance of Hib carriage in vaccinated populations. PMID:25926500