Coupling an electrospray source and a solids probe/chemical ionization source to a selected ion flow tube apparatus

International Nuclear Information System (INIS)

Melko, Joshua J.; Ard, Shaun G.; Shuman, Nicholas S.; Viggiano, Albert A.; Pedder, Randall E.; Taormina, Christopher R.

2015-01-01

A new ion source region has been constructed and attached to a variable temperature selected ion flow tube. The source features the capabilities of electron impact, chemical ionization, a solids probe, and electrospray ionization. The performance of the instrument is demonstrated through a series of reactions from ions created in each of the new source regions. The chemical ionization source is able to create H 3 O + , but not as efficiently as similar sources with larger apertures. The ability of this source to support a solids probe, however, greatly expands our capabilities. A variety of rhenium cations and dications are created from the solids probe in sufficient abundance to study in the flow tube. The reaction of Re + with O 2 proceeds with a rate constant that agrees with the literature measurements, while the reaction of Re 2 2+ is found to charge transfer with O 2 at about 60% of the collision rate; we have also performed calculations that support the charge transfer pathway. The electrospray source is used to create Ba + , which is reacted with N 2 O to create BaO + , and we find a rate constant that agrees with the literature

Monitoring of wine aging process by electrospray ionization mass spectrometry

Directory of Open Access Journals (Sweden)

Alexandra Christine Helena Frankland Sawaya

2011-09-01

Full Text Available The characterization of wine samples by direct insertion electrospray ionization mass spectrometry (ESI-MS, without pre-treatment or chromatographic separation, in a process denominated fingerprinting, has been applied to several samples of wine produced with grapes of the Pinot noir, Merlot and Cabernet Sauvignon varieties from the state o Rio Grande do Sul, in Brazil. The ESI-MS fingerprints of the samples detected changes which occurred during the aging process in the three grape varieties. Principal Component Analysis (PCA of the negative ion mode fingerprints was used to group the samples, pinpoint the main changes in their composition, and indicate marker ions for each group of samples.

Fragmentation study of iridoid glucosides through positive and negative electrospray ionization, collision-induced dissociation and tandem mass spectrometry.

Science.gov (United States)

Es-Safi, Nour-Eddine; Kerhoas, Lucien; Ducrot, Paul-Henri

2007-01-01

Mass spectrometric methodology based on the combined use of positive and negative electrospray ionization, collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS) has been applied to the mass spectral study of a series of six naturally occurring iridoids through in-source fragmentation of the protonated [M+H]+, deprotonated [M--H]- and sodiated [M+Na]+ ions. This led to the unambiguous determination of the molecular masses of the studied compounds and allowed CID spectra of the molecular ions to be obtained. Valuable structural information regarding the nature of both the glycoside and the aglycone moiety was thus obtained. Glycosidic cleavage and ring cleavages of both aglycone and sugar moieties were the major fragmentation pathways observed during CID, where the losses of small molecules, the cinnamoyl and the cinnamate parts were also observed. The formation of the ionized aglycones, sugars and their product ions was thus obtained giving information on their basic skeleton. The protonated, i.e. [M+H]+ and deprotonated [M--H]-, ions were found to fragment mainly by glycosidic cleavages. MS/MS spectra of the [M+Na]+ ions gave complementary information for the structural characterization of the studied compounds. Unlike the dissociation of protonated molecular ions, that of sodiated molecules also provided sodiated sugar fragments where the C0+ fragment corresponding to the glucose ion was obtained as base peak for all the studied compounds. Copyright (c) 2007 John Wiley & Sons, Ltd.

Ballpoint pen inks: characterization by positive and negative ion-electrospray ionization mass spectrometry for the forensic examination of writing inks.

Science.gov (United States)

Ng, Lay-Keow; Lafontaine, Pierre; Brazeau, Luc

2002-11-01

A method based on profiling of dye components by electrospray ionization mass spectrometry (ESI/MS) is described for the characterization of ballpoint pen inks. The method involves benzyl alcohol (30 microL) extraction of ink from paper. The extracts of ink lines 1 and 5 mm in length are used for direct ESI/MS analysis in positive and negative modes, respectively. The instrumental analysis takes 3 min. Basic and acid dyes in the inks are detected in the positive and negative modes, respectively, with each dye yielding one or two characteristic ion peaks. The mass spectrum, which is mainly a compositional signature of the dyes in the ink, was not affected by the type of paper from which the ink was extracted, or by natural ageing of the ink on document in the absence of light. However, exposure to fluorescent illumination caused dealkylation of polyalkylated basic dyes and resulted in changes in the homologous distribution of the dyes. In this study, a total of 44 blue inks, 23 black inks, and 10 red inks have been analyzed, and the mass spectra were used to establish a searchable library. ESI/MS analysis provides a simple and fast way to compare ink specimens and in combination with on-line library search permits rapid screening of inks for forensic document investigations.

Ion-neutral Clustering of Bile Acids in Electrospray Ionization Across UPLC Flow Regimes

Science.gov (United States)

Brophy, Patrick; Broeckling, Corey D.; Murphy, James; Prenni, Jessica E.

2018-02-01

Bile acid authentic standards were used as model compounds to quantitatively evaluate complex in-source phenomenon on a UPLC-ESI-TOF-MS operated in the negative mode. Three different diameter columns and a ceramic-based microfluidic separation device were utilized, allowing for detailed descriptions of bile acid behavior across a wide range of flow regimes and instantaneous concentrations. A custom processing algorithm based on correlation analysis was developed to group together all ion signals arising from a single compound; these grouped signals produce verified compound spectra for each bile acid at each on-column mass loading. Significant adduction was observed for all bile acids investigated under all flow regimes and across a wide range of bile acid concentrations. The distribution of bile acid containing clusters was found to depend on the specific bile acid species, solvent flow rate, and bile acid concentration. Relative abundancies of each cluster changed non-linearly with concentration. It was found that summing all MS level (low collisional energy) ions and ion-neutral adducts arising from a single compound improves linearity across the concentration range (0.125-5 ng on column) and increases the sensitivity of MS level quantification. The behavior of each cluster roughly follows simple equilibrium processes consistent with our understanding of electrospray ionization mechanisms and ion transport processes occurring in atmospheric pressure interfaces. [Figure not available: see fulltext.

METHOD 332.0: DETERMINATION OF PERCHLORATE IN DRINKING WATER BY ION CHROMATOGRAPHY WITH SUPPRESSED CONDUCTIVITY AND ELECTROSPRAY IONIZATION MASS SPECTROMETRY

Science.gov (United States)

This method is applicable to the identification and quantitation of perchlorate in raw and finished drinking waters. The approach used is ion chromatography with suppressed conductivity and electrospray ionization mass spectrometry (IC-ESI/MS)

Tandem mass spectrometry characteristics of polyester anions and cations formed by electrospray ionization.

Science.gov (United States)

Arnould, Mark A; Buehner, Rita W; Wesdemiotis, Chrys; Vargas, Rafael

2005-01-01

Electrospray ionization of polyesters composed of isophthalic acid and neopentyl glycol produces carboxylate anions in negative mode and mainly sodium ion adducts in positive mode. A tandem mass spectrometry (MS/MS) study of these ions in a quadrupole ion trap shows that the collisionally activated dissociation pathways of the anions are simpler than those of the corresponding cations. Charge-remote fragmentations predominate in both cases, but the spectra obtained in negative mode are devoid of the complicating cation exchange observed in positive mode. MS/MS of the Na(+) adducts gives rise to a greater number of fragments but not necessarily more structural information. In either positive or negative mode, polyester oligomers with different end groups fragment by similar mechanisms. The observed fragments are consistent with rearrangements initiated by the end groups. Single-stage ESI mass spectra also are more complex in positive mode because of extensive H/Na substitutions; this is also true for matrix-assisted laser desorption ionization (MALDI) mass spectra. Hence, formation and analysis of anions might be the method of choice for determining block length, end group structure and copolymer sequence, provided the polyester contains at least one carboxylic acid end group that is ionizable to anions.

A positive (negative) surface ionization source concept for radioactive ion beam generation

International Nuclear Information System (INIS)

Alton, G.D.; Mills, G.D.

1996-01-01

A novel, versatile, new concept, spherical-geometry, positive (negative) surface-ionization source has been designed and fabricated which will have the capability of generating both positive- and negative-ion beams without mechanical changes to the source. The source utilizes a highly permeable, high-work-function Ir ionizer (φ ≅ 5.29 eV) for ionizing highly electropositive atoms/molecules; while for negative-surface ionization, the work function is lowered by continually feeding a highly electropositive vapor through the ionizer matrix. The use of this technique to effect low work function surfaces for negative ion beam generation has the potential of overcoming the chronic poisoning effects experienced with LaB 6 while enhancing the probability for negative ion formation of atomic and molecular species with low to intermediate electron affinities. The flexibility of operation in either mode makes it especially attractive for radioactive ion beam (RIB) applications and, therefore, the source will be used as a complementary replacement for the high-temperature electron impact ionization sources presently in the use at the Holifield radioactive ion beam facility (HRIBF). The design features and operational principles of the source are described in this report. (orig.)

Liquid chromatography/negative electrospray ionization ion trap MS(2) mass spectrometry application for the determination of microcystins occurrence in Southern Portugal water reservoirs.

Science.gov (United States)

Rodrigues, M A; Reis, M P; Mateus, M C

2013-11-01

Microcystins (MCs) are toxins produced by cyanobacteria which are common organisms in the phytoplankton of eutrophic lakes, rivers and freshwater reservoirs. In the present work, a novel method of liquid chromatography-electrospray ion trap tandem mass spectrometry (LC/ESI/Ion trap-MS/MS), operated in the negative ionization mode, was developed for the analysis of these cyanotoxins. The method was applied to determine the amounts of total microcystins-LR, -YR and -RR in two water reservoirs in Southern Portugal, namely Alqueva and Beliche. A total of 30 water samples were analysed along 2011. Solid phase extraction (SPE) was used for sample cleaning-up and analyte enrichment. The extracted toxins were separated on a C18 column with a gradient of acetonitrile/water with 0.1% formic acid. Detection of microcystins was carried out using multiple reaction monitoring (MRM) in the negative polarity mode, as this method gave a higher selectivity. The MC-RR, YR and LR quantification limits were 17.9, 31.7 and 15.8 ng/L, respectively; quite below the limits recommended by WHO guidelines for drinking water (1 μg/L). Total MC highest concentrations were found in the warm months of June, July and September in Alqueva sampling sites, with concentrations of MC LR and RR ranging 17-344 and 25-212 ng/L, respectively, showing comparable results for MC-RR and LR and slightly lower concentration of MC-YR. Detected values for Beliche reservoir were below quantification limits. Copyright © 2013 Elsevier Ltd. All rights reserved.

Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

International Nuclear Information System (INIS)

Shukla, Anil; Bogdanov, Bogdan

2015-01-01

Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N 2 ). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi) n Li + , (HCOOLi) n Li m m+ , (HCOOLi) n HCOO − , and (HCOOLi) n (HCOO) m m− . Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi) 3 Li + being the most abundant and stable cluster ion. Fragmentations of singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi) 2 ) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi) 3 Li + as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability

Determination of short chain carboxylic acids in vegetable oils and fats using ion exclusion chromatography electrospray ionization mass spectrometry.

Science.gov (United States)

Viidanoja, Jyrki

2015-02-27

A new method for quantification of short chain C1-C6 carboxylic acids in vegetable oils and fats by employing Liquid Chromatography Mass Spectrometry (LC-MS) has been developed. The method requires minor sample preparation and applies non-conventional Electrospray Ionization (ESI) liquid phase chemistry. Samples are first dissolved in chloroform and then extracted using water that has been spiked with stable isotope labeled internal standards that are used for signal normalization and absolute quantification of selected acids. The analytes are separated using Ion Exclusion Chromatography (IEC) and detected with Electrospray Ionization Mass Spectrometry (ESI-MS) as deprotonated molecules. Prior to ionization the eluent that contains hydrochloric acid is modified post-column to ensure good ionization efficiency of the analytes. The averaged within run precision and between run precision were generally lower than 8%. The accuracy was between 85 and 115% for most of the analytes. The Lower Limit of Quantification (LLOQ) ranged from 0.006 to 7mg/kg. It is shown that this method offers good selectivity in cases where UV detection fails to produce reliable results. Copyright © 2015 Elsevier B.V. All rights reserved.

A high-efficiency positive (negative) surface ionization source for radioactive ion beam (abstract)a

International Nuclear Information System (INIS)

Alton, G.D.; Mills, G.D.

1996-01-01

A versatile, new concept, spherical-geometry, positive (negative) surface-ionization source has been designed and fabricated which will have the capability of generating both positive- and negative-ion beams without mechanical changes to the source. The source utilizes a highly permeable, high-work-function Ir ionizer (φ≡5.29 eV) for ionizing highly electropositive atoms/molecules; while for negative-surface ionization, the work function is lowered to φ≡1.43 eV by continually feeding cesium vapor through the ionizer matrix. The use of this technique for negative ion beam generation has the potential of overcoming the chronic poisoning effects experienced with LaB 6 while enhancing considerably the efficiency for negative surface ionization of atoms and molecules with intermediate electron affinities. The flexibility of operation in either mode makes it especially attractive for radioactive ion beam applications and, therefore, the source will be used as a complementary replacement for the high-temperature electron impact ionization sources presently in use at the Holifield radioactive beam facility. The design features and operational principles of the source will be described in this report. copyright 1996 American Institute of Physics

Separation of Opiate Isomers Using Electrospray Ionization and Paper Spray Coupled to High-Field Asymmetric Waveform Ion Mobility Spectrometry

Science.gov (United States)

Manicke, Nicholas E.; Belford, Michael

2015-05-01

One limitation in the growing field of ambient or direct analysis methods is reduced selectivity caused by the elimination of chromatographic separations prior to mass spectrometric analysis. We explored the use of high-field asymmetric waveform ion mobility spectrometry (FAIMS), an ambient pressure ion mobility technique, to separate the closely related opiate isomers of morphine, hydromorphone, and norcodeine. These isomers cannot be distinguished by tandem mass spectrometry. Separation prior to MS analysis is, therefore, required to distinguish these compounds, which are important in clinical chemistry and toxicology. FAIMS was coupled to a triple quadrupole mass spectrometer, and ionization was performed using either a pneumatically assisted heated electrospray ionization source (H-ESI) or paper spray, a direct analysis method that has been applied to the direct analysis of dried blood spots and other complex samples. We found that FAIMS was capable of separating the three opiate structural isomers using both H-ESI and paper spray as the ionization source.

Separation and identification of corticosterone metabolites by liquid chromatography--electrospray ionization mass spectrometry.

Science.gov (United States)

Miksík, I; Vylitová, M; Pácha, J; Deyl, Z

1999-04-16

High-performance liquid chromatography coupled to atmospheric pressure ionization-electrospray ionization mass spectrometry (API-ESI-MS) was investigated for the analysis of corticosterone metabolites; their characterization was obtained by combining the separation on Zorbax Eclipse XDB C18 column (eluted with a methanol-water-acetic acid gradient) with identification using positive ion mode API-ESI-MS and selected ion analysis. The applicability of this method was verified by monitoring the activity of steroid converting enzymes (20beta-hydroxysteroid dehydrogenase and 11beta-hydroxysteroid dehydrogenase) in avian intestines.

Dehydrodimerization of pterostilbene during electrospray ionization mass spectrometry

KAUST Repository

Raji, Misjudeen

2013-04-30

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

Effect of negative ions on current growth and ionizing wave propagation in air

International Nuclear Information System (INIS)

Kline, L.E.

1975-01-01

The spatiotemporal development of electron and ion densities, electric fields, and luminosity are calculated for electron pulse experiments in overvolted parallel-plane gaps by numerically solving continuity equations together with Poisson's equation. Experimental coefficients for primary ionization, cathode photoemission, photoionization, and luminosity are used. Unambiguous determination of the coefficients for attachment, detachment, and charge transfer is not possible from available experimental results. Therefore, the calculations are repeated for three sets of coefficients for these processes, corresponding to the following assumptions: unstable negative ions, stable negative ions, and no negative ions. The results of the calculations show, in each case, that the electron pulse initiates an avalanche which grows exponentially until the onset of space-charge effects. The calculated growth rate is strongly affected by the assumed attachment, detachment, and charge-transfer coefficients. When the total number of electrons in the avalanche reaches approx.10 8 , anode- and cathode-directed ionizing waves, or streamers, develop from the avalanche and produce a weakly ionized filamentary plasma. The calculated ionizing wave velocities are strongly increasing functions of the space-charge--enhanced electric field within the waves and are insensitive to the assumed attachment, detachment, and charge-transfer coefficients. The numerically calculated ionizing wave velocities are in approximate agreement with a simple analytical theory

Negative ion beam formation using thermal contact ionization type plasma source

Energy Technology Data Exchange (ETDEWEB)

Fukuura, Yoshiyuki; Murakami, Kazutugu; Masuoka, Toshio; Katsumata, Itsuo [Osaka City Univ. (Japan). Faculty of Engineering

1997-02-01

The small ion sources utilizing thermal ionization have been already developed, and at present, in order to increase ion yield, that being developed to the cylindrical plasma prototype having the inner surface of a Re foil cylinder as the ionization surface, and stably functioning at 3,000 K has been developed, and by using this plasma source, the research on the formation of various ions has been carried out. At present, the research on the formation of Li negative ion beam is carried out. The separation of negative ions from electrons is performed with the locally limited magnetic field using a small iron core electromagnet placed behind the electrostatic accelerating lens system. So for, the formation of about 2 {mu}A at maximum of negative ions was confirmed. It was decided to identify the kinds of ions by time of flight (TOF) process, and the various improvements for this purpose were carried out. The experimental setup, the structure of the plasma source, the circuits for TOF measurement and so on are explained. The experimental results are reported. The problems are the possibility of the formation of alkali metals, the resolution of the time axis of the TOF system and so on. (K.I.)

Combination of electrospray ionization, atmospheric pressure photoionization and laser desorption ionization Fourier transform ion cyclotronic resonance mass spectrometry for the investigation of complex mixtures – Application to the petroleomic analysis of bio-oils

Energy Technology Data Exchange (ETDEWEB)

Hertzog, Jasmine [LCP-A2MC, FR 2843 Institut Jean Barriol de Chimie et Physique Moléculaires et Biomoléculaires, FR 3624 Réseau National de Spectrométrie de Masse FT-ICR à très haut champ, Université de Lorraine, ICPM, 1 boulevard Arago, 57078 Metz Cedex 03 (France); Carré, Vincent, E-mail: vincent.carre@univ-lorraine.fr [LCP-A2MC, FR 2843 Institut Jean Barriol de Chimie et Physique Moléculaires et Biomoléculaires, FR 3624 Réseau National de Spectrométrie de Masse FT-ICR à très haut champ, Université de Lorraine, ICPM, 1 boulevard Arago, 57078 Metz Cedex 03 (France); Le Brech, Yann [LRGP, CNRS, Université de Lorraine, ENSIC, 1, Rue Grandville, 54000 Nancy (France); Mackay, Colin Logan [SIRCAMS, School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, Scotland (United Kingdom); Dufour, Anthony [LRGP, CNRS, Université de Lorraine, ENSIC, 1, Rue Grandville, 54000 Nancy (France); Mašek, Ondřej [UK Biochar Research Center, School of Geosciences, University of Edinburgh, Kings Buildings, Edinburgh, EH9 3JN (United Kingdom); and others

2017-05-29

The comprehensive description of complex mixtures such as bio-oils is required to understand and improve the different processes involved during biological, environmental or industrial operation. In this context, we have to consider how different ionization sources can improve a non-targeted approach. Thus, the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been coupled to electrospray ionization (ESI), laser desorption ionization (LDI) and atmospheric pressure photoionization (APPI) to characterize an oak pyrolysis bio-oil. Close to 90% of the all 4500 compound formulae has been attributed to C{sub x}H{sub y}O{sub z} with similar oxygen class compound distribution. Nevertheless, their relative abundance in respect with their double bound equivalent (DBE) value has evidenced significant differences depending on the ion source used. ESI has allowed compounds with low DBE but more oxygen atoms to be ionized. APPI has demonstrated the efficient ionization of less polar compounds (high DBE values and less oxygen atoms). The LDI behavior of bio-oils has been considered intermediate in terms of DBE and oxygen amounts but it has also been demonstrated that a significant part of the features are specifically detected by this ionization method. Thus, the complementarity of three different ionization sources has been successfully demonstrated for the exhaustive characterization by petroleomic approach of a complex mixture. - Highlights: • Non-targeted mass spectrometry by combining electrospray ionization, atmospheric pressure photoionization and laser/desorption ionization. • Exhaustive description of pyrolytic bio-oil components. • Distinction of sugaric derivatives, lignin derivatives and lipids contained in a woody-based pyrolytic bio-oil.

Control of Strobilurin Fungicides in Wheat Using Direct Analysis in Real Time Accurate Time-of-Flight and Desorption Electrospray Ionization Linear Ion Trap Mass Spectrometry

NARCIS (Netherlands)

Schurek, J.; Vaclavik, L.; Hooijerink, H.; Lacina, O.; Poustka, J.; Sharman, M.; Caldow, M.; Nielen, M.W.F.; Hajslova, J.

2008-01-01

Ambient mass spectrometry has been used for the analysis of strobilurin residues in wheat. The use of this novel, challenging technique, employing a direct analysis in a real time (DART) ion-source coupled with a time-of-flight mass spectrometer (TOF MS) and a desorption electrospray ionization

Comparison of Electrospray Ionization and Atmospheric Chemical Ionization Coupled with the Liquid Chromatography-Tandem Mass Spectrometry for the Analysis of Cholesteryl Esters

Directory of Open Access Journals (Sweden)

Hae-Rim Lee

2015-01-01

Full Text Available The approach of two different ionization techniques including electrospray ionization (ESI and atmospheric pressure chemical ionization (APCI coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS was tested for the analysis of cholesteryl esters (CEs. The retention time (RT, signal intensity, protonated ion, and product ion of CEs were compared between ESI and APCI. RT of CEs from both ionizations decreased with increasing double bonds, while it increased with longer carbon chain length. The ESI process generated strong signal intensity of precursor ions corresponding to [M+Na]+ and [M+NH4]+ regardless of the number of carbon chains and double bonds in CEs. On the other hand, the APCI process produced a protonated ion of CEs [M+H]+ with a weak signal intensity, and it is selectively sensitive to detect precursor ions of CEs with unsaturated fatty acids. The ESI technique proved to be effective in ionizing more kinds of CEs than the APCI technique.

Depth profiling of inks in authentic and counterfeit banknotes by electrospray laser desorption ionization/mass spectrometry.

Science.gov (United States)

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. Copyright © 2015 John Wiley & Sons, Ltd.

Study of cyclization of chelating compounds using electrospray ionization mass spectrometry

International Nuclear Information System (INIS)

Shi Ying; Campbell, J.A.

2000-01-01

Electrospray ionization mass spectrometry (ESI-MS) was used for the study of cyclization of organic chelating compounds (chelators). Four chelating compounds were studied: Symmetrical ethylenediaminediacetic acid (s-EDDA), Unsymmetrical ethylenediaminediacetic acid (u-EDDA), N-(2-hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), and N-(2-hydroxyethyl)iminodiacetic acid (HEIDA). The chelators were cyclized with treatments of acids and heating. The open and cyclized form of the chelators were semi-quantified by both positive and negative ion modes ESI-MS. The kinetics of chelator cyclization was studied as a function of reaction temperature and the pH of the matrix. The cyclization of s-EDDA was found to be a pseudo-first order reaction in s-EDDA and overall second order. The cyclizations of HEIDA and HEDTA are reversible reactions. Higher temperature and lower pH favors cyclization. (author)

Electrospray Ionization Mass Spectrometric Analysis of Highly Reactive Glycosyl Halides

Directory of Open Access Journals (Sweden)

Lajos Kovács

2012-07-01

Full Text Available Highly reactive glycosyl chlorides and bromides have been analysed by a routine mass spectrometric method using electrospray ionization and lithium salt adduct-forming agents in anhydrous acetonitrile solution, providing salient lithiated molecular ions [M+Li]⁺, [2M+Li]⁺ etc. The role of other adduct-forming salts has also been evaluated. The lithium salt method is useful for accurate mass determination of these highly sensitive compounds.

Positive and negative ion mode comparison for the determination of DNA/peptide noncovalent binding sites through the formation of "three-body" noncovalent fragment ions.

Science.gov (United States)

Brahim, Bessem; Tabet, Jean-Claude; Alves, Sandra

2018-02-01

Gas-phase fragmentation of single strand DNA-peptide noncovalent complexes is investigated in positive and negative electrospray ionization modes.Collision-induced dissociation experiments, performed on the positively charged noncovalent complex precursor ions, have confirmed the trend previously observed in negative ion mode, i.e. a high stability of noncovalent complexes containing very basic peptidic residues (i.e. R > K) and acidic nucleotide units (i.e. Thy units), certainly incoming from the existence of salt bridge interactions. Independent of the ion polarity, stable noncovalent complex precursor ions were found to dissociate preferentially through covalent bond cleavages of the partners without disrupting noncovalent interactions. The resulting DNA fragment ions were found to be still noncovalently linked to the peptides. Additionally, the losses of an internal nucleic fragment producing "three-body" noncovalent fragment ions were also observed in both ion polarities, demonstrating the spectacular salt bridge interaction stability. The identical fragmentation patterns (regardless of the relative fragment ion abundances) observed in both polarities have shown a common location of salt bridge interaction certainly preserved from solution. Nonetheless, most abundant noncovalent fragment ions (and particularly three-body ones) are observed from positively charged noncovalent complexes. Therefore, we assume that, independent of the preexisting salt bridge interaction and zwitterion structures, multiple covalent bond cleavages from single-stranded DNA/peptide complexes rely on an excess of positive charges in both electrospray ionization ion polarities.

ELECTROSPRAY, TECHNIQUE AND APPLICATIONS

NARCIS (Netherlands)

BRUINS, AP

Electrospray makes use of ions present in electrically charged droplets in an aerosol. The generation of an aerosol by electrospray has already been published by Zeleny in 1917. The feasibility of electrospray as an ionization technique was demonstrated by Fenn and coworkers, and by a group of

Ultra pressure liquid chromatography-negative electrospray ionization mass spectrometry determination of twelve halobenzoquinones at ng/L levels in drinking water.

Science.gov (United States)

Huang, Rongfu; Wang, Wei; Qian, Yichao; Boyd, Jessica M; Zhao, Yuli; Li, Xing-Fang

2013-05-07

We report here the characterization of twelve halobenzoquinones (HBQs) using electrospray ionization (ESI) high resolution quadrupole time-of-flight mass spectrometry. The high resolution negative ESI spectra of the twelve HBQs formed two parent ions, [M + H(+) + 2e(-)], and the radical M(-•). The intensities of these two parent ions are dependent on their chemical structures and on instrumental parameters such as the source temperature and flow rate. The characteristic ions of the HBQs were used to develop an ultra pressure liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method. At the UPLC flow rate (400 μL/min) and under the optimized ESI conditions, eleven HBQs showed the stable and abundant transitions [M + H(+) + 2e(-)] → X(-) (X(-) representing Cl(-), Br(-), or I(-)), while dibromo-dimethyl-benzoquinone (DBDMBQ) showed only the transition of M(-•) → Br(-). The UPLC efficiently separates all HBQs including some HBQ isomers, while the MS/MS offers exquisite limits of detection (LODs) at subng/mL levels for all HBQs except DBDMBQ. Combined with solid phase extraction (SPE), the method LOD is down to ng/L. The results from analysis of authentic samples demonstrated that the SPE-UPLC-MS/MS method is reliable, fast, and sensitive for the identification and quantification of the twelve HBQs in drinking water.

Cleavage reactions of the complex ions derived from self-complementary deoxydinucleotides and alkali-metal ions using positive ion electrospray ionization with tandem mass spectrometry.

Science.gov (United States)

Xiang, Yun; Abliz, Zeper; Takayama, Mitsuo

2004-05-01

The dissociation reactions of the adduct ions derived from the four self-complementary deoxydinucleotides, d(ApT), d(TpA), d(CpG), d(GpC), and alkali-metal ions were studied in detail by positive ion electrospray ionization multiple-stage mass spectrometry (ESI-MS(n)). For the [M + H](+) ions of the four deoxydinucleotides, elimination of 5'-terminus base or loss of both of 5'-terminus base and a deoxyribose were the major dissociation pathway. The ESI-MS(n) spectra showed that Li(+), Na(+), and Cs(+) bind to deoxydinucleotides mainly by substituting the H(+) of phosphate group, and these alkali-metal ions preferred to bind to pyrimidine bases rather than purine bases. For a given deoxydinucleotide, the dissociation pathway of [M + K](+) ions differed clearly from that of [M + Li](+), [M + Na](+), and [M + Cs](+) ions. Some interesting and characteristic cleavage reactions were observed in the product-ion spectra of [M + K](+) ions, including direct elimination of deoxyribose and HPO(3) from molecular ions. The fragmentation behavior of the [M + K](+) and [M + W](+) (W = Li, Na, Cs) adduct ions depend upon the sequence of bases, the interaction between alkali-metal ions and nucleobases, and the steric hindrance caused by bases.

Simultaneous determination of thirteen flavonoids from Xiaobuxin-Tang extract using high-performance liquid chromatography coupled with electrospray ionization mass spectrometry.

Science.gov (United States)

Cen, Meifeng; Ruan, Jinxiu; Huang, Lihua; Zhang, Zhenqing; Yu, Nengjiang; Zhang, Youzhi; Cheng, Xuange; Xiong, Xiaohong; Wang, Guixiang; Zang, Linquan; Wang, Sujun

2015-11-10

A simple and reliable high performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) analysis method was established to simultaneously determine thirteen flavonoids of Xiaobuxing-Tang in intestine perfusate, namely onpordin, 3'-O-methylorobol, glycitein, patuletin, genistein, luteolin, quercetin, nepitrin, quercimeritrin, daidzin, patulitrin, quercetagitrin and 3-glucosylisorhamnetin. Detection was performed on a quadrupole mass spectrometer equipped with an electrospray ionization (ESI) source operating in negative ionization mode. Negative ion ESI was used to form deprotonated molecules at m/z 315 for onpordin, m/z 299 for 3'-O-methylorobol, m/z 283 for glycitein, m/z 331 for patuletin, m/z 269 for genistein, m/z 285 for luteolin, m/z 301 for quercetin, m/z 477 for nepitrin, m/z 463 for quercimeritrin, m/z 461 for daidzin, m/z 493 for patulitrin, m/z 479 for quercetagitrin, m/z 477 for 3-glucosylisorhamnetin and m/z 609.2 for rutin. The linearity, sensitivity, selectivity, repeatability, accuracy, precision, recovery and matrix effect of the assay were evaluated. The proposed method was successfully applied to simultaneous determination of these thirteen flavonoids, and using this method, the intestinal absorption profiles of thirteen flavonoids were preliminarily predicted. Copyright © 2015 Elsevier B.V. All rights reserved.

Matrix-assisted laser desorption/ionization time-of-flight and nano-electrospray ionization ion trap mass spectrometric characterization of 1-cyano-2-substituted-benz[f]isoindole derivatives of peptides for fluorescence detection

DEFF Research Database (Denmark)

Linnemayr, K; Brückner, A; Körner, R

1999-01-01

A series of hexa- to decapeptides (molecular mass range 800-1200) were labeled with naphthalene-2,3-dicarboxaldehyde, which preferentially reacts with the primary amino groups of a peptide. A highly stable peptide conjugate is formed, which allows selective analysis by fluorescence at excitation...... and emission wavelengths of 420 and 490 nm, respectively. After removal of unreacted compounds, the peptide conjugates were characterized by matrix-assisted laser desorption/ionization (MALDI) time-of-flight and nano-electrospray ionization (ESI) ion trap mass spectrometry. They readily form both [M + H]+ ions...... by MALDI and both [M + H]+ and [M + 2H]2+ ions by ESI. Furthermore, the fragmentation behavior of the N-terminally tagged peptides, exhibiting an uncharged N-terminus, was investigated applying post-source decay fragmentation with a curved field reflector and collision-induced dissociation...

Synthesis and Electrospray Ionization Mass Spectra of N-(1,3,2-Dioxaphosphorinan-2-ylmethyl)thiophosphoramidates

Institute of Scientific and Technical Information of China (English)

MIAO,Zhi-Wei; FU,Cui-Rong; WANG,Bin; CUI,Zhan-Wei; ZHANG,Jian-Feng; CHEN,Ru-Yu

2007-01-01

N-(1,3,2-Dioxaphosphorinan-2-ylmethyl) thiophosphoramidates were synthesized and determined by NMR spectra and positive ion electrospray ionization mass spectrometry (ESI-MS) in conjunction with tandem mass spectrometry (MS/MS). The fragmentation pathways were investigated. The results show that these characteristic ions in ESI mass spectra are useful in the structural determination of N-(1,3,2-dioxaphosphorinan-2-ylmethyl)thiophosphoramidates.

Electrospray ionization and matrix assisted laser desorption/ionization mass spectrometry: powerful analytical tools in recombinant protein chemistry

DEFF Research Database (Denmark)

Andersen, Jens S.; Svensson, B; Roepstorff, P

1996-01-01

Electrospray ionization and matrix assisted laser desorption/ionization are effective ionization methods for mass spectrometry of biomolecules. Here we describe the capabilities of these methods for peptide and protein characterization in biotechnology. An integrated analytical strategy is presen......Electrospray ionization and matrix assisted laser desorption/ionization are effective ionization methods for mass spectrometry of biomolecules. Here we describe the capabilities of these methods for peptide and protein characterization in biotechnology. An integrated analytical strategy...... is presented encompassing protein characterization prior to and after cloning of the corresponding gene....

Application of liquid chromatography-electrospray ionization mass spectrometry for study of steroid-converting enzymes.

Science.gov (United States)

Miksík, Ivan; Mikulíková, Katerina; Pácha, Jirí; Kucka, Marek; Deyl, Zdenek

2004-02-05

A high-performance liquid chromatography-atmospheric pressure ionization-electrospray ionization mass spectrometry (HPLC-API-ESI-MS) method was developed for the analysis of steroids in a study of steroid-converting enzymes. Separations ware done on a Zorbax Eclipse XDB-C18 column (eluted with a linear methanol-water-acetic acid gradient) and identification of the steroids involved was done by API-ESI-MS using positive ion mode and extracted ion analysis. The applicability of the present method for studying steroid metabolism was proven in assaying two steroid-converting enzymes (20beta-hydroxysteroid dehydrogenase and 11beta-hydroxysteroid dehydrogenase) in various biological samples (rat and chicken intestine, chicken oviduct).

Analysis of antibiotics from liquid sample using electrospray ionization-ion mobility spectrometry

International Nuclear Information System (INIS)

Li Shu; Jia Jian; Gao Xiaoguang; He Xiuli; Li Jianping

2012-01-01

Highlights: ► The reduced mobilities of 18 antibiotics are determined. ► Establishing antibiotic mass-mobility correlation using (12,4) potential model. ► Multi-component characteristics of antibiotics can be revealed using ESI-IMS. ► Most mixtures of antibiotics can be analyzed using ESI-IMS. ► The detection limit of amoxicillin is 70 pg. - Abstract: The recent findings of antibiotic residues in aquatic environment at trace level have gained much concern for the detrimental effect on ecological and human health due to bacterial resistance. Here, the feasibility of using electrospray ionization ion mobility spectrometry (ESI-IMS) for analysis antibiotics in liquid sample is demonstrated. Reduced mobilities and collision cross sections of 18 antibiotics are experimentally measured and compared with theoretical values according to mass-mobility correlation. Gentamicin is used as an example to investigate the capability of ESI-IMS for multi-component analysis of antibiotics. Mixtures of antibiotics at different concentrations are analyzed. The estimated detection limit for amoxicillin is 0.7 mg L −1 (70 pg) and the linear range of response maintains over two orders. This method will be a potential technique for the analysis of antibiotics in aquatic environment.

Measurement of total acid number (TAN) and TAN boiling point distribution in petroleum products by electrospray ionization mass spectrometry.

Science.gov (United States)

Qian, Kuangnan; Edwards, Kathleen E; Dechert, Gary J; Jaffe, Stephen B; Green, Larry A; Olmstead, William N

2008-02-01

We report a new method for rapid measurement of total acid number (TAN) and TAN boiling point (BP) distribution for petroleum crude and products. The technology is based on negative ion electrospray ionization mass spectrometry (ESI-MS) for selective ionization of petroleum acid and quantification of acid structures and molecular weight distributions. A chip-based nanoelectrospray system enables microscale (boiling point distributions of TAN values can be calculated from the composition. The rapid measurement of TAN BP distributions by ESI is demonstrated for a series of high-TAN crudes and distillation cuts. TAN values determined by the technique agree well with those by the titration method. The distributed properties compare favorably with those measured by distillation and measurement of TAN of corresponding cuts.

Automated Gain Control and Internal Calibration With External Ion Accumulation Capillary liquid chromatography-electrospray ionization-fourier transform ion cyclotron resonance.

Energy Technology Data Exchange (ETDEWEB)

Belov, Mikhail E.(VISITORS); Zhang, Rui (BATTELLE (PACIFIC NW LAB)); Strittmatter, Eric F.(BATTELLE (PACIFIC NW LAB)); Prior, David C.(BATTELLE (PACIFIC NW LAB)); Tang, Keqi (BATTELLE (PACIFIC NW LAB)); Smith, Richard D.(BATTELLE (PACIFIC NW LAB))

2003-08-15

When combined with capillary LC separations, Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FTICR MS) has increasingly been applied for advanced characterization of proteolytic digests. Incorporation of external (to the ICR cell) ion accumulation multipoles with FTICR for ion pre selection and accumulation has enhanced the dynamic range, sensitivity and duty cycle of measurements. However, the highly variable ion production rate from an LC separation can result in overfilling of the external trap, resulting in m/z discrimination and fragmentation of peptide ions. An excessive space charge trapped in the ICR cell causes significant shifts in the detected ion cyclotron frequencies, reducing the achievable mass measurement accuracy (MMA) for protein identification. To eliminate m/z discrimination in the external ion trap, further increase the duty cycle and improve MMA, we developed a capability for data-dependent adjustment of ion accumulation times in the course of an LC separation, referred to as Automated Gain Control (AGC), in combination with low kinetic energy gated ion trapping and internal calibration using a dual-channel electrodynamic ion funnel. The system was initially evaluated in the analysis of a 0.5 mg/mL tryptic digest of bovine serum albumin. The implementation of LC/ESI/AGC/FTICR with internal calibration gave rise to a {approx} 10-fold increase in the number of identified tryptic peptides within mass measurement accuracy of 2 ppm as compared to that detected during the conventional LC/FTICR run with a fixed ion accumulation time and external calibration.

Accurate and rapid modeling of iron–bleomycin-induced DNA damage using tethered duplex oligonucleotides and electrospray ionization ion trap mass spectrometric analysis

OpenAIRE

Harsch, Andreas; Marzilli, Lisa A.; Bunt, Richard C.; Stubbe, Joanne; Vouros, Paul

2000-01-01

Bleomycin B2 (BLM) in the presence of iron [Fe(II)] and O2 catalyzes single-stranded (ss) and double-stranded (ds) cleavage of DNA. Electrospray ionization ion trap mass spectrometry was used to monitor these cleavage processes. Two duplex oligonucleotides containing an ethylene oxide tether between both strands were used in this investigation, allowing facile monitoring of all ss and ds cleavage events. A sequence for site-specific binding and cleavage by Fe–BLM was incorporated into each an...

Fast quantitative detection of cocaine in beverages using nanoextractive electrospray ionization tandem mass spectrometry.

Science.gov (United States)

Hu, Bin; Peng, Xuejiao; Yang, Shuiping; Gu, Haiwei; Chen, Huanwen; Huan, Yanfu; Zhang, Tingting; Qiao, Xiaolin

2010-02-01

Without any sample pretreatment, effervescent beverage fluids were manually sprayed into the primary ion plume created by using a nanoelectrospray ionization source for direct ionization, and the analyte ions of interest were guided into an ion trap mass spectrometer for tandem mass analysis. Functional ingredients (e.g., vitamins, taurine, and caffeine, etc.) and spiked impurity (e.g., cocaine) in various beverages, such as Red Bull energy drink, Coco-cola, and Pepsi samples were rapidly identified within 1.5 s. The limit of detection was found to be 7-15 fg (S/N = 3) for cocaine in different samples using the characteristic fragment (m/z 150) observed in the MS(3) experiments. Typical relative standard deviation and recovery of this method were 6.9%-8.6% and 104%-108% for direct analysis of three actual samples, showing that nanoextractive electrospray ionization tandem mass spectrometry is a useful technique for fast screening cocaine presence in beverages. 2010. Published by Elsevier Inc.

Characterization of Ni(II) complexes of Schiff bases of amino acids and (S)-N-(2-benzoylphenyl)-1-benzylpyrrolidine-2-carboxamide using ion trap and QqTOF electrospray ionization tandem mass spectrometry

NARCIS (Netherlands)

Jirasko, Robert; Holcapek, Michal; Kolarova, Lenka; Nadvornik, Milan; Popkov, Alexander

This work demonstrates the application of electrospray ionization mass spectrometry (ESI-MS) using two different mass analyzers, ion trap and hybrid quadrupole time-of-flight (QqTOF) mass analyzer, for the structural characterization of Ni(II) complexes of Schiff bases of

Detection of chlorinated and brominated byproducts of drinking water disinfection using electrospray ionization-high-field asymmetric waveform ion mobility spectrometry-mass spectrometry.

Science.gov (United States)

Ells, B; Barnett, D A; Froese, K; Purves, R W; Hrudey, S; Guevremont, R

1999-10-15

The lower limit of detection for low molecular weight polar and ionic analytes using electrospray ionization-mass spectrometry (ESI-MS) is often severely compromised by an intense background that obscures ions of trace components in solution. Recently, a new technique, referred to as high-field asymmetric waveform ion mobility spectrometry (FAIMS), has been shown to separate gas-phase ions at atmospheric pressure and room temperature. A FAIMS instrument is an ion filter that may be tuned, by control of electrical voltages, to continuously transmit selected ions from a complex mixture. This capability offers significant advantages when FAIMS is coupled with ESI, a source that generates a wide variety of ions, including solvent clusters and salt adducts. In this report, the tandem arrangement of ESI-FAIMS-MS is used for the analysis of haloacetic acids, a class of disinfection byproducts regulated by the US EPA. FAIMS is shown to effectively discriminate against background ions resulting from the electrospray of tap water solutions containing the haloacetic acids. Consequently, mass spectra are simplified, the selectivity of the method is improved, and the limits of detection are lowered compared with conventional ESI-MS. The detection limits of ESI-FAIMS-MS for six haloacetic acids ranged between 0.5 and 4 ng/mL in 9:1 methanol/tap water (5 and 40 ng/mL in the original tap water samples) with no preconcentration, derivatization, or chromatographic separation prior to analysis.

Simultaneous determination of asperosaponin VI and its active metabolite hederagenin in rat plasma by liquid chromatography-tandem mass spectrometry with positive/negative ion-switching electrospray ionization and its application in pharmacokinetic study.

Science.gov (United States)

Zhu, He; Ding, Li; Shakya, Shailendra; Qi, Xiemin; Hu, Linlin; Yang, Xiaolin; Yang, Zhonglin

2011-11-15

A new liquid chromatography-tandem mass spectrometry (LC-MS/MS) method operated in the positive/negative electrospray ionization (ESI) switching mode has been developed and validated for the simultaneous determination of asperosaponin VI and its active metabolite hederagenin in rat plasma. After addition of internal standards diazepam (for asperosaponin VI) and glycyrrhetic acid (for hederagenin), the plasma sample was deproteinized with acetonitrile, and separated on a reversed phase C18 column with a mobile phase of methanol (solvent A)-0.05% glacial acetic acid containing 10 mM ammonium acetate and 30 μM sodium acetate (solvent B) using gradient elution. The detection of target compounds was done in multiple reaction monitoring (MRM) mode using a tandem mass spectrometry equipped with positive/negative ion-switching ESI source. At the first segment, the MRM detection was operated in the positive ESI mode using the transitions of m/z 951.5 ([M+Na](+))→347.1 for asperosaponin VI and m/z 285.1 ([M+H](+))→193.1 for diazepam for 4 min, then switched to the negative ESI mode using the transitions of m/z 471.3 ([M-H](-))→471.3 for hederagenin and m/z 469.4 ([M-H](-))→425.4 for glycyrrhetic acid, respectively. The sodiated molecular ion [M+Na](+) at m/z 951.5 was selected as the precursor ion for asperosaponin VI, since it provided better sensitivity compared to the deprotonated and protonated molecular ions. Sodium acetate was added to the mobile phase to make sure that abundant amount of the sodiated molecular ion of asperosaponin VI could be produced, and more stable and intensive mass response of the product ion could be obtained. For the detection of hederagenin, since all of the mass responses of the fragment ions were very weak, the deprotonated molecular ion [M-H](-)m/z 471.3 was employed as both the precursor ion and the product ion. But the collision energy was still used for the MRM, in order to eliminate the influences induced by the interference

Quantitation of tamsulosin in human plasma by liquid chromatography-electrospray ionization mass spectrometry.

Science.gov (United States)

Din, Li; Li, Limin; Tao, Ping; Yang, Jin; Zhang, Zhengxing

2002-02-05

A highly sensitive method for quantitation of tamsulosin in human plasma using 1-(2,6-dimethyl-3-hydroxylphenoxy)-2-(3,4-methoxyphenylethylamino)-propane hydrochloride as the internal standard (I.S.) was established using liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS). After alkalization with saturated sodium bicarbonate, plasma were extracted by ethyl acetate and separated by HPLC on a C18 reversed-phase column using a mobile phase of methanol-water-acetic acid-triethylamine (620:380:1.5:1.5, v/v). Analytes were quantitated using positive electrospray ionization in a quadrupole spectrometer. LC-ESI-MS was performed in the selected ion monitoring (SIM) mode using target ions at m/z 228 for tamsulosin and m/z 222 for the I.S. Calibration curves, which were linear over the range 0.2-30 ng/ml, were analyzed contemporaneously with each batch of samples, along with low (0.5 ng/ml), medium (3 ng/ml) and high (30 ng/ml) quality control samples. The intra- and inter-assay variability ranged from 2.14 to 8.87% for the low, medium and high quality control samples. The extraction recovery of tamsulosin from plasma was in the range of 84.2-94.5%. The method has been used successfully to study tamsulosin pharmacokinetics in adult humans.

Analysis of antibiotics from liquid sample using electrospray ionization-ion mobility spectrometry

Energy Technology Data Exchange (ETDEWEB)

Shu, Li; Jian, Jia; Xiaoguang, Gao; Xiuli, He [State Key Laboratory of Transducer Technology, Institute of Electronics, Chinese Academy of Sciences, Beijing 100190 (China); Li Jianping, E-mail: jpli@mail.ie.ac.cn [State Key Laboratory of Transducer Technology, Institute of Electronics, Chinese Academy of Sciences, Beijing 100190 (China)

2012-03-30

Highlights: Black-Right-Pointing-Pointer The reduced mobilities of 18 antibiotics are determined. Black-Right-Pointing-Pointer Establishing antibiotic mass-mobility correlation using (12,4) potential model. Black-Right-Pointing-Pointer Multi-component characteristics of antibiotics can be revealed using ESI-IMS. Black-Right-Pointing-Pointer Most mixtures of antibiotics can be analyzed using ESI-IMS. Black-Right-Pointing-Pointer The detection limit of amoxicillin is 70 pg. - Abstract: The recent findings of antibiotic residues in aquatic environment at trace level have gained much concern for the detrimental effect on ecological and human health due to bacterial resistance. Here, the feasibility of using electrospray ionization ion mobility spectrometry (ESI-IMS) for analysis antibiotics in liquid sample is demonstrated. Reduced mobilities and collision cross sections of 18 antibiotics are experimentally measured and compared with theoretical values according to mass-mobility correlation. Gentamicin is used as an example to investigate the capability of ESI-IMS for multi-component analysis of antibiotics. Mixtures of antibiotics at different concentrations are analyzed. The estimated detection limit for amoxicillin is 0.7 mg L{sup -1} (70 pg) and the linear range of response maintains over two orders. This method will be a potential technique for the analysis of antibiotics in aquatic environment.

Determination of triacylglycerol regioisomers using electrospray ionization-quadrupole ion trap mass spectrometry with a kinetic method.

Science.gov (United States)

Leveque, Nathalie L; Acheampong, Akwasi; Heron, Sylvie; Tchapla, Alain

2012-04-13

The kinetic method was applied to differentiate and quantify mixtures of regioisomeric triacylglycerols (TAGs) by generating and mass selecting alkali ion bound metal dimeric clusters with a TAG chosen as reference (ref) and examining their competitive dissociations in a quadrupole ion trap mass spectrometer. This methodology readily distinguished pairs of regioisomers (AAB/ABA) such as LLO/LOL, OOP/OPO and SSP/SPS and consequently distinguished sn-1/sn-3, sn-2 substituents on the glycerol backbone. The dimeric complex ions [ref, Li, TAG((AAB and/or ABA))](+) generated by electrospray ionization mass spectrometry were subjected to collision induced dissociation causing competitive loss of either the neutral TAG reference (ref) leading to [Li(AAB and/or ABA)](+) or the neutral TAG molecule (TAG((AAB and/or ABA))) leading to [ref, Li](+). The ratio of the two competitive dissociation rates, defined by the product ion branching ratio (R(iso)), was related via the kinetic method to the regioisomeric composition of the investigated TAG mixture. In this work, a linear correlation was established between composition of the mixture of each TAG regioisomer and the logarithm of the branching ratio for competitive fragmentation. Depending on the availability of at least one TAG regioisomer as standard, the kinetic method and the standard additions method led to the quantitative analysis of natural TAG mixtures. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrospray Ionization Mass Spectrometry: A Technique to Access the Information beyond the Molecular Weight of the Analyte

Science.gov (United States)

Banerjee, Shibdas; Mazumdar, Shyamalava

2012-01-01

The Electrospray Ionization (ESI) is a soft ionization technique extensively used for production of gas phase ions (without fragmentation) of thermally labile large supramolecules. In the present review we have described the development of Electrospray Ionization mass spectrometry (ESI-MS) during the last 25 years in the study of various properties of different types of biological molecules. There have been extensive studies on the mechanism of formation of charged gaseous species by the ESI. Several groups have investigated the origin and implications of the multiple charge states of proteins observed in the ESI-mass spectra of the proteins. The charged analytes produced by ESI can be fragmented by activating them in the gas-phase, and thus tandem mass spectrometry has been developed, which provides very important insights on the structural properties of the molecule. The review will highlight recent developments and emerging directions in this fascinating area of research. PMID:22611397

Electrospray ionization mass spectrometry: a technique to access the information beyond the molecular weight of the analyte.

Science.gov (United States)

Banerjee, Shibdas; Mazumdar, Shyamalava

2012-01-01

The Electrospray Ionization (ESI) is a soft ionization technique extensively used for production of gas phase ions (without fragmentation) of thermally labile large supramolecules. In the present review we have described the development of Electrospray Ionization mass spectrometry (ESI-MS) during the last 25 years in the study of various properties of different types of biological molecules. There have been extensive studies on the mechanism of formation of charged gaseous species by the ESI. Several groups have investigated the origin and implications of the multiple charge states of proteins observed in the ESI-mass spectra of the proteins. The charged analytes produced by ESI can be fragmented by activating them in the gas-phase, and thus tandem mass spectrometry has been developed, which provides very important insights on the structural properties of the molecule. The review will highlight recent developments and emerging directions in this fascinating area of research.

Differentiation of isomeric 2-aryldimethyltetrahydro-5-quinolinones by electron ionization and electrospray ionization mass spectrometry.

Science.gov (United States)

Kumar, Ch Dinesh; Chary, V Naresh; Dinesh, A; Reddy, P S; Srinivas, K; Gayatri, G; Sastry, G N; Prabhakar, S

2011-10-15

A series of isomeric 2-aryl-6,6-dimethyltetrahydro-5-quinolinones (set I) and 2-aryl-7,7-dimethyltetrahydro-5-quinolinones (set II) were studied under positive ion electron ionization (EI) and electrospray ionization (ESI) techniques. Under EI conditions, the molecular ions were found to be less stable in set I isomers, and they resulted in abundant fragment ions, i.e., [M-CH(3)](+), [M-CO](+.), [M-HCO](+), [M-(CH(3),CO)](+), and [M-(CH(3),CH(2)O)](+), when compared with set II isomers. In addition, the set I isomers showed specific fragment ions corresponding to [M-OH](+) and [M-OCH(3)](+). The retro-Diels-Alder (RDA) product ion was always higher in set II isomers. The ESI mass spectra produced [M + H](+) ions, and their decomposition showed favorable loss of CH(3) radical, CH(4) and C(2)H(6) molecules in set I isomers. The set II isomers, however, showed predominant RDA product ions, and specific loss of H(2)O. The selectivity in EI and ESI was attributed to the instability of set I isomers by the presence of a gem-dimethyl group at the α-position, and it was supported by the data from model compounds without a gem-dimethyl group. Density functional theory (DFT) calculations successfully corroborated the fragmentation pathways for diagnostic ions. This study revealed the effect of a gem-dimethyl group located at the α-position to the carbonyl having aromatic/unsaturated carbon on the other side of the carbonyl group. Copyright © 2011 John Wiley & Sons, Ltd.

Developing a Vacuum Electrospray Source To Implement Efficient Atmospheric Sampling for Miniature Ion Trap Mass Spectrometer.

Science.gov (United States)

Yu, Quan; Zhang, Qian; Lu, Xinqiong; Qian, Xiang; Ni, Kai; Wang, Xiaohao

2017-12-05

The performance of a miniature mass spectrometer in atmospheric analysis is closely related to the design of its sampling system. In this study, a simplified vacuum electrospray ionization (VESI) source was developed based on a combination of several techniques, including the discontinuous atmospheric pressure interface, direct capillary sampling, and pneumatic-assisted electrospray. Pulsed air was used as a vital factor to facilitate the operation of electrospray ionization in the vacuum chamber. This VESI device can be used as an efficient atmospheric sampling interface when coupled with a miniature rectilinear ion trap (RIT) mass spectrometer. The developed VESI-RIT instrument enables regular ESI analysis of liquid, and its qualitative and quantitative capabilities have been characterized by using various solution samples. A limit of detection of 8 ppb could be attained for arginine in a methanol solution. In addition, extractive electrospray ionization of organic compounds can be implemented by using the same VESI device, as long as the gas analytes are injected with the pulsed auxiliary air. This methodology can extend the use of the proposed VESI technique to rapid and online analysis of gaseous and volatile samples.

Effects of liquid post-column addition in electrospray ionization performance in supercritical fluid chromatography-mass spectrometry.

Science.gov (United States)

Akbal, Laura; Hopfgartner, Gérard

2017-09-29

In supercritical fluid chromatography coupled to atmospheric pressure ionization mass spectrometry (SFC-MS), the use of a make-up post-column is almost mandatory to avoid analyte precipitation, especially when using low percentage of modifier (supercritical conditions (1mL/min 40°C, 150bar) to gaseous state (room temperature, atmospheric pressure), the CO 2 expands around 430 times, contributing to almost 5% of the nebulizing process. In positive mode, the presence of ammonium ions either in the mobile phase or in the make-up did significantly increase the MS signal, even at basic apparent pH. The ionization performance of electrospray is influenced by the acidic buffer power of the carbon dioxide, and was found to be restricted in the apparent pH range of 3.8-7.2 in the various conditions investigated. This may challenge sensitive detection in negative mode, as illustrated for bosentan. The use of DMSO as make-up additive (up to 30%) showed a simplification of the full scan spectrum regarding the adducts. Finally, the optimization of make-up composition leads to an enhancement up to a factor of 69 on the electrospray MS response signal, for the SFC-SRM/MS analysis of HIV protease inhibitors in plasma extracted from Dried Plasma Spots. Copyright © 2017 Elsevier B.V. All rights reserved.

Characterization of primaquine imidazolidin-4-ones with antimalarial activity by electrospray ionization-ion trap mass spectrometry

Science.gov (United States)

Vale, Nuno; Moreira, Rui; Gomes, Paula

2008-02-01

The extensive characterization by electrospray ionization-ion trap mass spectrometry (ESI-MSn) of 20 imidazolidin-4-ones derived from the antimalarial primaquine was well obtained. These compounds are being under investigation as potential antimalarials, as they have been previously found to be active against rodent P. berghei malaria and to be highly stable under physiological conditions. Experiments by collision-induced dissociation (CID) in the nozzle-skimmer region or by tandem-MS have shown the title compounds to be remarkably stable. Mechanisms are proposed to explain the major fragmentations observed in ESI-MSn experiments. Overall, this work represents an unprecedented contribution to a deeper insight into imidazolidin-4-one antimalarials based on a classic 8-aminoquinolinic scaffold. Data herein reported and discussed may be an useful guide for future studies on therapeutically relevant molecules possessing either the 8-aminoquinoline or the imidazolidin-4-one motifs.

Negative chemical ionization mass spectrometry

International Nuclear Information System (INIS)

Smit, A.L.C.

1979-01-01

This thesis describes some aspects of Negative Chemical Ionization (NCI) mass spectrometry. The reasons for the growing interest in NCI are: (i) to extend the basic knowledge of negative ions and their reactions in the gas phase; (ii) to investigate whether or not this knowledge of negative ions can be used successfully to elucidate the structure of molecules by mass spectrometry. (Auth.)

Rapid in situ detection of alkaloids in plant tissue under ambient conditions using desorption electrospray ionization.

Science.gov (United States)

Talaty, Nari; Takáts, Zoltán; Cooks, R Graham

2005-12-01

Desorption electrospray ionization (DESI) mass spectrometry is applied to the in situ detection of alkaloids in the tissue of poison hemlock (Conium maculatum), jimsonweed (Datura stramonium) and deadly nightshade (Atropa belladonna). The experiment is carried out by electrospraying micro-droplets of solvent onto native or freshly-cut plant tissue surfaces. No sample preparation is required and the mass spectra are recorded under ambient conditions, in times of a few seconds. The impact of the sprayed droplets on the surface produces gaseous ions from organic compounds originally present in the plant tissue. The effects of operating parameters, including the electrospray high voltage, heated capillary temperature, the solvent infusion rate and the carrier gas pressure on analytical performance are evaluated and optimized. Different types of plant material are analyzed including seeds, stems, leaves, roots and flowers. All the previously reported alkaloids have been detected in C. maculatum, while fifteen out of nineteen known alkaloids for D. stramonium and the principal alkaloids of A. belladonna were also identified. All identifications were confirmed by tandem mass spectrometry. Results obtained show similar mass spectra, number of alkaloids, and signal intensities to those obtained when extraction and separation processes are performed prior to mass spectrometric analysis. Evidence is provided that DESI ionization occurs by both a gas-phase ionization process and by a droplet pick-up mechanism. Quantitative precision of DESI is compared with conventional electrospray ionization mass spectrometry (after sample workup) and the RSD values for the same set of 25 dicotyledonous C. maculatum seeds (one half of each seed analyzed by ESI and the other by DESI) are 9.8% and 5.2%, respectively.

Combination of electrospray ionization, atmospheric pressure photoionization and laser desorption ionization Fourier transform ion cyclotronic resonance mass spectrometry for the investigation of complex mixtures - Application to the petroleomic analysis of bio-oils.

Science.gov (United States)

Hertzog, Jasmine; Carré, Vincent; Le Brech, Yann; Mackay, Colin Logan; Dufour, Anthony; Mašek, Ondřej; Aubriet, Frédéric

2017-05-29

The comprehensive description of complex mixtures such as bio-oils is required to understand and improve the different processes involved during biological, environmental or industrial operation. In this context, we have to consider how different ionization sources can improve a non-targeted approach. Thus, the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been coupled to electrospray ionization (ESI), laser desorption ionization (LDI) and atmospheric pressure photoionization (APPI) to characterize an oak pyrolysis bio-oil. Close to 90% of the all 4500 compound formulae has been attributed to C x H y O z with similar oxygen class compound distribution. Nevertheless, their relative abundance in respect with their double bound equivalent (DBE) value has evidenced significant differences depending on the ion source used. ESI has allowed compounds with low DBE but more oxygen atoms to be ionized. APPI has demonstrated the efficient ionization of less polar compounds (high DBE values and less oxygen atoms). The LDI behavior of bio-oils has been considered intermediate in terms of DBE and oxygen amounts but it has also been demonstrated that a significant part of the features are specifically detected by this ionization method. Thus, the complementarity of three different ionization sources has been successfully demonstrated for the exhaustive characterization by petroleomic approach of a complex mixture. Copyright © 2017 Elsevier B.V. All rights reserved.

Internal energy effects on the solvation and reactivity of multiply charged biomolecules for electrospray ionization mass spectroscopy. [Bovine ubiquitin

Energy Technology Data Exchange (ETDEWEB)

Light-Wahl, K.J.; Winger, B.E.; Rockwood, A.L.; Smith, R.D.

1992-06-01

Mild (capillary) interface conditions which do not completely desolvate the ions of proteins in electrospray ionization mass spectrometry (ESI-MS) may be required to probe the higher order structures and weak associations. For the small protein bovine ubiquitin, two ion distributions (unsolvated ions and unresolved solvated ions) were observed. The resolvable solvation for leucine-enkephalin with methanol and water shows that the use of countercurrent N{sub 2} flow at the capillary affects the solvation observed. 2 figs. (DLC)

A qualitative study of amlodipine and its related compounds by electrospray ionization tandem mass spectrometry.

Science.gov (United States)

Gibbons, John; Pugh, Jonathan; Dimopoulos-Italiano, Gina; Pike, Richard

2006-01-01

A comprehensive structural analysis of amlodipine and certain related compounds was performed by electrospray ionization tandem mass spectrometry. Triple quadrupole and quadrupole time-of-flight instruments were used to provide collision-induced dissociation and accurate mass measurement for selected product and second-generation product ions. A unique ion rearrangement was observed, which was found to be characteristic of certain dihydropyridines. This study provides a fundamental understanding of the fragmentation of these compounds. The structural elucidation of an unknown impurity is presented as an example. Copyright (c) 2006 John Wiley & Sons, Ltd.

Chemical characterization of synthetic cannabinoids by electrospray ionization FT-ICR mass spectrometry.

Science.gov (United States)

Kill, Jade B; Oliveira, Izabela F; Tose, Lilian V; Costa, Helber B; Kuster, Ricardo M; Machado, Leandro F; Correia, Radigya M; Rodrigues, Rayza R T; Vasconcellos, Géssica A; Vaz, Boniek G; Romão, Wanderson

2016-09-01

The synthetic cannabinoids (SCs) represent the most recent advent of the new psychotropic substances (NPS) and has become popularly known to mitigate the effects of the Δ(9)-THC. The SCs are dissolved in organic solvents and sprayed in a dry herbal blend. However, little information is reported on active ingredients of SCs as well as the excipients or diluents added to the herbal blend. In this work, the direct infusion electrospray ionization Fourier transform ion cyclotron mass spectrometry technique (ESI-FT-ICR MS) was applied to explore the chemical composition of nine samples of herbal extract blends, where a total of 11 SCs (UR-144, JWH-073, XLR-11, JWH-250, JWH-122, AM-2201, AKB48, JWH-210, JWH-081, MAM-2201 and 5F-AKB48) were identified in the positive ionization mode, ESI(+), and other 44 chemical species (saturated and unsaturated fatty acids, sugars, flavonoids, etc.) were detected in the negative ionization mode, ESI(-). Additionally, CID experiments were performed, and fragmentation pathways were proposed to identify the connectivity of SCs. Thus, the direct infusion ESI-FT-ICR MS technique is a powerful tool in forensic chemistry that enables the rapid and unequivocal way for the determination of molecular formula, the degree of unsaturation (DBE-double bond equivalent) and exact mass (<1ppm) of a total of 55 chemical species without the prior separation step. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Electrospray ionization tandem mass spectrometry of ammonium cationized polyethers.

Science.gov (United States)

Nasioudis, Andreas; Heeren, Ron M A; van Doormalen, Irene; de Wijs-Rot, Nicolette; van den Brink, Oscar F

2011-05-01

Quaternary ammonium salts (Quats) and amines are known to facilitate the MS analysis of high molar mass polyethers by forming low charge state adduct ions. The formation, stability, and behavior upon collision-induced dissociation (CID) of adduct ions of polyethers with a variety of Quats and amines were studied by electrospray ionization quadrupole time-of-flight, quadrupole ion trap, and linear ion trap tandem mass spectrometry (MS/MS). The linear ion trap instrument was part of an Orbitrap hybrid mass spectrometer that allowed accurate mass MS/MS measurements. The Quats and amines studied were of different degree of substitution, structure, and size. The stability of the adduct ions was related to the structure of the cation, especially the amine's degree of substitution. CID of singly/doubly charged primary and tertiary ammonium cationized polymers resulted in the neutral loss of the amine followed by fragmentation of the protonated product ions. The latter reveals information about the monomer unit, polymer sequence, and endgroup structure. In addition, the detection of product ions retaining the ammonium ion was observed. The predominant process in the CID of singly charged quaternary ammonium cationized polymers was cation detachment, whereas their doubly charged adduct ions provided the same information as the primary and tertiary ammonium cationized adduct ions. This study shows the potential of specific amines as tools for the structural elucidation of high molar mass polyethers. © American Society for Mass Spectrometry, 2011

Focused Electrospray Deposition for Matrix-assisted Laser Desorption/Ionization Mass Spectrometry

International Nuclear Information System (INIS)

Jeong, Kyung Hwan; Seo, Jong Cheol; Yoon, Hye Joo; Shin, Seung Koo

2010-01-01

Focused electrospray (FES) deposition method is presented for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. FES ion optics consists of two cylindrical focusing electrodes capped with a truncated conical electrode through which an electrospray emitter passes along the cylindrical axis. A spray of charged droplets is focused onto a sample well on a MALDI target plate under atmospheric pressure. The shape and size distributions of matrix crystals are visualized by scanning electron microscope and the mass spectra are obtained by time-of-flight mass spectrometry. Angiotensin II, bradykinin, and substance P are used as test samples, while α-cyano-4-hydroxycinnamic acid and dihydroxybenzoic acid are employed as matrices. FES of a sample/matrix mixture produces fine crystal grains on a 1.3 mm spot and reproducibly yields the mass spectra with little shot-to-shot and spot-to-spot variations. Although FES greatly stabilizes the signals, the space charge due to matrix ions limits the detection sensitivity of peptides. To avoid the space charge problem, we adopted a dual FES/FES mode, which separately deposits matrix and sample by FES in sequence. The dual FES/FES mode reaches the detection sensitivity of 0.88 amol, enabling ultrasensitive detection of peptides by homogeneously depositing matrix and sample under atmospheric pressure

Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry

Science.gov (United States)

Colizza, Kevin; Mahoney, Keira E.; Yevdokimov, Alexander V.; Smith, James L.; Oxley, Jimmie C.

2016-11-01

Efforts to analyze trace levels of cyclic peroxides by liquid chromatography/mass spectrometry gave evidence that acetonitrile suppressed ion formation. Further investigations extended this discovery to ketones, linear peroxides, esters, and possibly many other types of compounds, including triazole and menadione. Direct ionization suppression caused by acetonitrile was observed for multiple adduct types in both electrospray ionization and atmospheric pressure chemical ionization. The addition of only 2% acetonitrile significantly decreased the sensitivity of analyte response. Efforts to identify the mechanism were made using various nitriles. The ion suppression was reduced by substitution of an acetonitrile hydrogen with an electron-withdrawing group, but was exacerbated by electron-donating or steric groups adjacent to the nitrile. Although current theory does not explain this phenomenon, we propose that polar interactions between the various functionalities and the nitrile may be forming neutral aggregates that manifest as ionization suppression.

Fragmentation pathways and structural characterization of organophosphorus compounds related to the Chemical Weapons Convention by electron ionization and electrospray ionization tandem mass spectrometry.

Science.gov (United States)

Hosseini, Seyed Esmaeil; Saeidian, Hamid; Amozadeh, Ali; Naseri, Mohammad Taghi; Babri, Mehran

2016-12-30

For unambiguous identification of Chemical Weapons Convention (CWC)-related chemicals in environmental samples, the availability of mass spectra, interpretation skills and rapid microsynthesis of suspected chemicals are essential requirements. For the first time, the electron ionization single quadrupole and electrospray ionization tandem mass spectra of a series of O-alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates (Scheme 1, cpd 4) were studied for CWC verification purposes. O-Alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates were prepared through a microsynthetic method and were analyzed using electron ionization and electrospray ionization mass spectrometry with gas and liquid chromatography, respectively, as MS-inlet systems. General EI and ESI fragmentation pathways were proposed and discussed, and collision-induced dissociation studies of the protonated derivatives of these compounds were performed to confirm proposed fragment ion structures by analyzing mass spectra of deuterated analogs. Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as McLafferty rearrangement, hydrogen rearrangement and a previously unknown intramolecular electrophilic aromatic substitution reaction. The EI and ESI fragmentation routes of the synthesized compounds 4 were investigated with the aim of detecting and identifying CWC-related chemicals during on-site inspection and/or off-site analysis and toxic chemical destruction monitoring. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Plume collimation for laser ablation electrospray ionization mass spectrometry

Science.gov (United States)

Vertes, Akos; Stolee, Jessica A.

2014-09-09

In various embodiments, a device may generally comprise a capillary having a first end and a second end; a laser to emit energy at a sample in the capillary to ablate the sample and generate an ablation plume in the capillary; an electrospray apparatus to generate an electrospray plume to intercept the ablation plume to produce ions; and a mass spectrometer having an ion transfer inlet to capture the ions. The ablation plume may comprise a collimated ablation plume. The device may comprise a flow cytometer. Methods of making and using the same are also described.

Spatially resolved chemical analysis of cicada wings using laser-ablation electrospray ionization (LAESI) imaging mass spectrometry (IMS).

Science.gov (United States)

Román, Jessica K; Walsh, Callee M; Oh, Junho; Dana, Catherine E; Hong, Sungmin; Jo, Kyoo D; Alleyne, Marianne; Miljkovic, Nenad; Cropek, Donald M

2018-03-01

Laser-ablation electrospray ionization (LAESI) imaging mass spectrometry (IMS) is an emerging bioanalytical tool for direct imaging and analysis of biological tissues. Performing ionization in an ambient environment, this technique requires little sample preparation and no additional matrix, and can be performed on natural, uneven surfaces. When combined with optical microscopy, the investigation of biological samples by LAESI allows for spatially resolved compositional analysis. We demonstrate here the applicability of LAESI-IMS for the chemical analysis of thin, desiccated biological samples, specifically Neotibicen pruinosus cicada wings. Positive-ion LAESI-IMS accurate ion-map data was acquired from several wing cells and superimposed onto optical images allowing for compositional comparisons across areas of the wing. Various putative chemical identifications were made indicating the presence of hydrocarbons, lipids/esters, amines/amides, and sulfonated/phosphorylated compounds. With the spatial resolution capability, surprising chemical distribution patterns were observed across the cicada wing, which may assist in correlating trends in surface properties with chemical distribution. Observed ions were either (1) equally dispersed across the wing, (2) more concentrated closer to the body of the insect (proximal end), or (3) more concentrated toward the tip of the wing (distal end). These findings demonstrate LAESI-IMS as a tool for the acquisition of spatially resolved chemical information from fragile, dried insect wings. This LAESI-IMS technique has important implications for the study of functional biomaterials, where understanding the correlation between chemical composition, physical structure, and biological function is critical. Graphical abstract Positive-ion laser-ablation electrospray ionization mass spectrometry coupled with optical imaging provides a powerful tool for the spatially resolved chemical analysis of cicada wings.

Efficacy of bacterial bioremediation: Demonstration of complete incorporation of hydrocarbons into membrane phospholipids from Rhodococcus hydrocarbon degrading bacteria by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Rodgers, R.P.; Blumer, E.N.; Emmett, M.R.; Marshall, A.G.

2000-02-01

The authors present a method and example to establish complete incorporation of hydrocarbons into membrane phospholipids of putatively bioremediative bacteria. Bacteria are grown on minimal media containing a specified carbon source, either natural abundance or enriched. After extraction (but no other prior separation) of the membrane lipids, electrospray ionization yields a negative-ion FT-ICR mass spectrum containing prominent phospholipid parent ions. If {sup 13}C-enriched hydrocarbon incorporation is complete, then the mass of the parent ion will increase by n Da, in which n is the number of its constituent carbon atoms; moreover, the {sup 13}C isotopic distribution pattern will be reversed. The identities of the constituent fatty acids and polar headgroup are obtained by collisional dissociation (MS/MS), and their extent of {sup 13}C incorporation determined individually. The method is demonstrated for Rhodococcus rhodochrous (ATCC No. 53968), for which all 44 carbons of a representative phosphatidylinositol are shown to derive from the hydrocarbon source. Interestingly, although only C{sub 16} and C{sub 18} alkanes are provided in the growth medium, the bacteria synthesize uniformly enriched C16:0 and C19:0 fatty acids.

Electrospray Ionization Mechanisms for Large Polyethylene Glycol Chains Studied Through Tandem Ion Mobility Spectrometry

Science.gov (United States)

Larriba, Carlos; de la Mora, Juan Fernandez; Clemmer, David E.

2014-08-01

Ion mobility mass spectrometry (IMS-MS) is used to investigate the abundance pattern, n z (m) of Poly-(ethyleneglycol) (PEG) electrosprayed from water/methanol as a function of mass and charge state. We examine n z (m) patterns from a diversity of solution cations, primarily dimethylammonium and triethylammonium. The ability of PEG chains to initially attach to various cations in the spraying chamber, and to retain them (or not) on entering the MS, provide valuable clues on the ionization mechanism. Single chains form in highly charged and extended shapes in most buffers. But the high initial charge they hold under atmospheric pressure is lost on transit to the vacuum system for large cations. In contrast, aggregates of two or more chains carry in all buffers at most the Rayleigh charge of a water drop of the same volume. This shows either that they form via Dole's charge residue mechanism, or that highly charged and extended aggregates are ripped apart by Coulombic repulsion. IMS-IMS experiments in He confirm these findings, and provide new mechanistic insights on the stability of aggregates. When collisionally activated, initially globular dimers are stable. However, slightly nonglobular dimers projecting out a linear appendix are segregated into two monomeric chains. The breakup of a charged dimer is therefore a multi-step process, similar to the Fenn-Consta polymer extrusion mechanism. The highest activation barrier is associated to the first step, where a short chain segment carrying a single charge escapes (ion-evaporates) from a charged drop, leading then to gradual field extrusion of the whole chain out of the drop.

Relationships between structure, ionization profile and sensitivity of exogenous anabolic steroids under electrospray ionization and analysis in human urine using liquid chromatography-tandem mass spectrometry.

Science.gov (United States)

Cha, Eunju; Kim, Sohee; Kim, Hee Won; Lee, Kang Mi; Kim, Ho Jun; Kwon, Oh-Seung; Lee, Jaeick

2016-04-01

The relationships between the ionization profile, sensitivity, and structures of 64 exogenous anabolic steroids (groups I-IV) was investigated under electrospray ionization (ESI) conditions. The target analytes were ionized as [M + H](+) or [M + H-nH2 O](+) in the positive mode, and these ions were used as precursor ions for selected reaction monitoring analysis. The collision energy and Q3 ions were optimized based on the sensitivity and selectivity. The limits of detection (LODs) were 0.05-20 ng/mL for the 64 steroids. The LODs for 38 compounds, 14 compounds and 12 compounds were in the range of 0.05-1, 2-5 and 10-20 ng/mL, respectively. Steroids including the conjugated keto-functional group at C3 showed good proton affinity and stability, and generated the [M + H](+) ion as the most abundant precursor ion. In addition, the LODs of steroids using the [M + H](+) ion as the precursor ion were mostly distributed at low concentrations. In contrast, steroids containing conjugated/unconjugated hydroxyl functional groups at C3 generated [M + H - H2 O](+) or [M + H - 2H2 O](+) ions, and these steroids showed relatively high LODs owing to poor stability and multiple ion formation. An LC-MS/MS method based on the present ionization profile was developed and validated for the determination of 78 steroids (groups I-V) in human urine. Copyright © 2015 John Wiley & Sons, Ltd.

Online monitoring of chemical reactions by polarization-induced electrospray ionization.

Science.gov (United States)

Meher, Anil Kumar; Chen, Yu-Chie

2016-09-21

Polarization-induced electrospray ionization (PI-ESI) is a simple technique for instant generation of gas-phase ions directly from a microliter-sized droplet for mass spectrometric analysis. A sample droplet was placed over a dielectric substrate and in proximity (2-3 mm) to the inlet of a mass spectrometer. Owing to the polarization effect induced by the high electric field provided by the mass spectrometer, the droplet was polarized and the electrospray was generated from the apex of the droplet. The polarization-induced electrospray could last for tens of seconds, which was sufficiently long to monitor fast reactions occurring within few seconds. Thus, we demonstrated the feasibility of using the droplet-based PI-ESI MS for the online monitoring of fast reactions by simply mixing two droplets (5-10 μL) containing reactants on a dielectric substrate placed in front of a mass spectrometer applied with a high voltage (-4500 V). Schiff base reactions and oxidation reactions that can generate intermediates/products within a few seconds were selected as the model reactions. The ionic reaction species generated from intermediates and products can be simultaneously monitored by PI-ESI MS in real time. We also used this approach to selectively detect acetone from a urine sample, in which acetone was derivatized in situ. In addition, the possibility of using this approach for quantitative analysis of acetone from urine samples was examined. Copyright © 2016 Elsevier B.V. All rights reserved.

Coupling of gas chromatography and electrospray ionization high resolution mass spectrometry for the analysis of anabolic steroids as trimethylsilyl derivatives in human urine.

Science.gov (United States)

Cha, Eunju; Jeong, Eun Sook; Cha, Sangwon; Lee, Jaeick

2017-04-29

In this study, gas chromatography (GC) was interfaced with high resolution mass spectrometry (HRMS) with electrospray ionization source (ESI) and the relevant parameters were investigated to enhance the ionization efficiency. In GC-ESI, the distances (x-, y- and z) and angle between the ESI needle, GC capillary column and MS orifice were set to 7 (x-distance), 4 (y-distance), and 1 mm (z-distance). The ESI spray solvent, acid modifier and nebulizer gas flow were methanol, 0.1% formic acid and 5 arbitrary units, respectively. Based on these results, analytical conditions for GC-ESI/HRMS were established. In particular, the results of spray solvent flow indicated a concentration-dependent mechanism (peak dilution effect), and other parameters also greatly influenced the ionization performance. The developed GC-ESI/HRMS was then applied to the analysis of anabolic steroids as trimethylsilyl (TMS) derivatives in human urine to demonstrate its application. The ionization profiles of TMS-derivatized steroids were investigated and compared with those of underivatized steroids obtained from gas chromatography-electrospray ionization/mass spectrometry (GC-ESI/MS) and liquid chromatography-electrospray ionization/mass spectrometry (LC-ESI/MS). The steroids exhibited ionization profiles based on their structural characteristics, regardless of the analyte phase or derivatization. Groups I and II with conjugated or unconjugated keto functional groups at C3 generated the [M+H] + and [M+H-TMS] + ions, respectively. On the other hand, Groups III and IV gave rise to the characteristic fragment ions [M+H-TMS-H 2 O] + and [M+H-2TMS-H 2 O] + , corresponding to loss of a neutral TMS·H 2 O moiety from the protonated molecular ion by in-source dissociation. To the best of our knowledge, this is the first study to successfully ionize and analyze steroids as TMS derivatives using ESI coupled with GC. The present system has enabled the ionization of TMS derivatives under ESI conditions

Gas-phase copper and silver complexes with phosphorothioate and phosphorodithioate pesticides investigated using electrospray ionization mass spectrometry.

Science.gov (United States)

Mustapha, Adetayo M; Pasilis, Sofie P

2015-01-01

Efforts to improve agricultural productivity have led to a growing dependency on organophosphorus pesticides. Phosphorothioate and phosphorodithioate pesticides are organophosphorus pesticide subclasses with widespread application for the control of insects feeding on vegetables and fruits. However, even low doses of these pesticides can cause neurological problems in humans; thus, their determination and monitoring in agricultural foodstuffs is important for human health. Phosphorothioate and phosphorodithioate pesticides may be poorly ionized during electrospray, adversely affecting limits of detection. These pesticides can form complexes with Cu(2+) and Ag(+) , however, potentially improving ionization. In the present work, we used electrospray ionization/mass spectrometry (ESI/MS) to study fenitrothion, parathion, diazinon, and malathion coordination complexes with silver and copper ions. Stable 1 : 1 and 1 : 2 metal/pesticide complexes were detected. Mass spectra acquired from pesticide solutions containing Ag(+) or Cu(2+) showed a significant increase in signal-to-background ratio over those acquired from solutions containing only the pesticides, with Ag(+) improving detection more effectively than Cu(2+). Addition of Ag(+) to a pesticide solution improved the limit of detection by ten times. The relative affinity of each pesticide for Ag(+) was related to complex stability, following the order diazinon > malathion > fenitrothion > parathion. The formation of Ag(+)-pesticide complexes can significantly improve the detection of phosphorothioate and phosphorodithioate pesticides using ESI/MS. The technique could potentially be used in reactive desorption electrospray ionization/mass spectrometry to detect phosphorothioate and phosphorodithioate pesticides on fruit and vegetable skins. Copyright © 2015 John Wiley & Sons, Ltd.

Chemical speciation analysis for bromine in tap water by ion chromatography/inductively coupled plasma-mass spectrometry and electrospray ionization-mass spectrometry

International Nuclear Information System (INIS)

Kurata, Keigo; Suzuki, Yoshinari; Furuta, Naoki

2010-01-01

Bromide compounds in tap water were measured by using a hyphenated technique of ion chromatography coupled with inductively coupled plasma - mass spectrometry (IC/ICP-MS) and electrospray ionization mass spectrometry (ESI-MS). We identified bromide ion (Br - ), bromate ion (BrO 3 - ), bromochloroacetic acid (BCAA), dibromoacetic acid (DBAA) and bromodichloroacetic acid (BDCAA) by standard addition methods with IC/ICP-MS. Moreover, we identified BCAA and BDCAA by ESI-MS after separation with IC. Br - , BrO 3 - , BCAA, DBAA and BDCAA in tap water collected from around Tokyo area were quantified by IC/ICP-MS. The maximum concentration of BrO 3 - (1.8 ng mL -1 ) was observed in tap water collected from Bunkyo-ku, although this concentration was lower than 10 ng mL -1 , which is the regulated concentration in Japan. DBAA, which is regulated by United States Environmental Protection Agency, was detected in tap water collected from all sites, except for Ome. However, since BrO 3 - and DBAA are toxic, it is necessary to continue monitoring bromide compounds in tap water. (author)

Probing uranyl(VI) speciation in the presence of amidoxime ligands using electrospray ionization mass spectrometry.

Science.gov (United States)

Mustapha, Adetayo M; Pasilis, Sofie P

2013-10-15

Extraction processes using poly(acrylamidoxime) resins are being developed to extract uranium from seawater. The main complexing agents in these resins are thought to be 2,6-dihydroxyiminopiperidine (DHIP) and N(1),N(5)-dihydroxypentanediimidamide (DHPD), which form strong complexes with uranyl(VI) at the pH of seawater. It is important to understand uranyl(VI) speciation in the presence of these and similar amidoxime ligands to understand factors affecting uranyl(VI) adsorption to the poly(acrylamidoxime) resins. Experiments were carried out in positive ion mode on a quadrupole ion trap mass spectrometer equipped with an electrospray ionization source. The ligands investigated were DHIP, DHPD, and N(1),N(2)-dihydroxyethanediimidamide (DHED). DHED and DHPD differ only in the number of carbons separating the oxime groups. The effects on the mass spectra of changes in uranyl(VI):ligand ratio, pH, and ligand type were examined. DHIP binds uranyl(VI) more effectively than DHPD or DHED in the pH range investigated, forming ions derived from solution-phase species with uranyl(VI):DHIP stoichiometries of 1:1, 1:2, and 2:3. The 2:3 uranyl(VI):DHIP complex appears to be a previously undescribed solution species. Ions related to uranyl(VI):DHPD complexes were detected in very low abundance. DHED is a more effective complexing agent for uranyl(VI) than DHPD, forming ions having uranyl(VI):DHED stoichiometries of 1:1, 1:2, 1:3, and 2:3. This study presents a first look at the solution chemistry of uranyl(VI)-amidoxime complexes using electrospray ionization mass spectrometry. The appearance of previously undescribed solution species suggests that the uranyl-amidoxime system is a rich and relatively complex one, requiring a more in-depth investigation. Copyright © 2013 John Wiley & Sons, Ltd.

Improving N-Glycan Coverage using HPLC-MS with Electrospray Ionization at Subambient Pressure

Energy Technology Data Exchange (ETDEWEB)

Marginean, Ioan; Kronewitter, Scott R.; Moore, Ronald J.; Slysz, Gordon W.; Monroe, Matthew E.; Anderson, Gordon A.; Tang, Keqi; Smith, Richard D.

2012-10-01

Human serum glycan profiling with mass spectrometry (MS) has been employed to study several disease conditions and is demonstrating promise for e.g. clinical biomarker discovery. However, the poor glycan ionization efficiency and the large dynamic range of glycan concentrations in human sera hinder comprehensive profiling. In particular, large glycans are problematic because they are present at low concentrations and prone to fragmentation. Here we show that the sub-ambient pressure ionization with nanoelectrospray (SPIN)-MS can expand the serum glycome profile when compared with the conventional atmospheric pressure electrospray ionization (ESI)-MS with a heated capillary inlet. Notably, the ions generated by the SPIN interface were observed at higher charge states for 50% of the annotated glycans. Out of a total of 130 detected glycans, 34 were only detected with the SPIN-MS, resulting in improved coverage of glycan families as well as of glycans with larger numbers of labile monosaccharides.

High-performance ion mobility spectrometry with direct electrospray ionization (ESI-HPIMS) for the detection of additives and contaminants in food

International Nuclear Information System (INIS)

Midey, Anthony J.; Camacho, Amanda; Sampathkumaran, Jayanthi; Krueger, Clinton A.; Osgood, Mark A.; Wu, Ching

2013-01-01

Graphical abstract: -- Highlights: •A new ESI source was built for direct ionization from syringe. •Phthalates, food dyes, and sweeteners detected with high-performance IMS. •Phthalates directly detected in cola, soy bubble tea matrices with simple treatment. -- Abstract: High-performance ion mobility spectrometry (HPIMS) with an electrospray ionization (ESI) source detected a series of food contaminants and additive compounds identified as critical to monitoring the safety of food samples. These compounds included twelve phthalate plasticizers, legal and illegal food and cosmetic dyes, and artificial sweeteners that were all denoted as detection priorities. HPIMS separated and detected the range of compounds with a resolving power better than 60 in both positive and negative ion modes, comparable to the commonly used high-performance liquid chromatography (HPLC) methods, but with most acquisition times under a minute. The reduced mobilities, K 0 , have been determined, as have the linear response ranges for ESI-HPIMS, which are 1.5–2 orders of magnitude for concentrations down to sub-ng μL −1 levels. At least one unique mobility peak was seen for two subsets of the phthalates grouped by the country where they were banned. Furthermore, ESI-HPIMS successfully detected low nanogram levels of a phthalate at up to 30 times lower concentration than international detection levels in both a cola matrix and a soy-based bubble tea beverage using only a simplified sample treatment. A newly developed direct ESI source (Directspray) was combined with HPIMS to detect food-grade dyes and industrial dye adulterants, as well as the sweeteners sodium saccharin and sodium cyclamate, with the same good performance as with the phthalates. However, the Directspray method eliminated sources of carryover and decreased the time between sample runs. Limits-of-detection (LOD) for the analyte standards were estimated to be sub-ng μL −1 levels without extensive sample handling

High-performance ion mobility spectrometry with direct electrospray ionization (ESI-HPIMS) for the detection of additives and contaminants in food

Energy Technology Data Exchange (ETDEWEB)

Midey, Anthony J., E-mail: anthony.midey@excellims.com; Camacho, Amanda; Sampathkumaran, Jayanthi; Krueger, Clinton A.; Osgood, Mark A.; Wu, Ching

2013-12-04

Graphical abstract: -- Highlights: •A new ESI source was built for direct ionization from syringe. •Phthalates, food dyes, and sweeteners detected with high-performance IMS. •Phthalates directly detected in cola, soy bubble tea matrices with simple treatment. -- Abstract: High-performance ion mobility spectrometry (HPIMS) with an electrospray ionization (ESI) source detected a series of food contaminants and additive compounds identified as critical to monitoring the safety of food samples. These compounds included twelve phthalate plasticizers, legal and illegal food and cosmetic dyes, and artificial sweeteners that were all denoted as detection priorities. HPIMS separated and detected the range of compounds with a resolving power better than 60 in both positive and negative ion modes, comparable to the commonly used high-performance liquid chromatography (HPLC) methods, but with most acquisition times under a minute. The reduced mobilities, K{sub 0}, have been determined, as have the linear response ranges for ESI-HPIMS, which are 1.5–2 orders of magnitude for concentrations down to sub-ng μL{sup −1} levels. At least one unique mobility peak was seen for two subsets of the phthalates grouped by the country where they were banned. Furthermore, ESI-HPIMS successfully detected low nanogram levels of a phthalate at up to 30 times lower concentration than international detection levels in both a cola matrix and a soy-based bubble tea beverage using only a simplified sample treatment. A newly developed direct ESI source (Directspray) was combined with HPIMS to detect food-grade dyes and industrial dye adulterants, as well as the sweeteners sodium saccharin and sodium cyclamate, with the same good performance as with the phthalates. However, the Directspray method eliminated sources of carryover and decreased the time between sample runs. Limits-of-detection (LOD) for the analyte standards were estimated to be sub-ng μL{sup −1} levels without extensive

A positive (negative) surface ionization source concept for RIB generation

International Nuclear Information System (INIS)

Alton, G.D.; Mills, G.D.

1995-01-01

A novel, versatile, new concept, spherical-geometry, positive (negative) surface-ionization source has been designed and fabricated which will have the capability of generating both positive- and negative-ion beams without mechanical changes to the source. The source utilizes a highly permeable, high-work-function Ir ionizer (φ∼ = 5.29 eV) for ionizing highly electropositive atoms/molecules; while for negative-surface ionization, the work function is lowered to φ ∼ = 1.43 eV by continually feeding cesium vapor through the ionizer matrix. The use of Cs to effect low work function surfaces for negative ion beam generation has the potential of overcoming the chronic poisoning effects experienced with LaB 6 while enhancing the probability for negative ion formation of atomic and molecular species with low to intermediate electron affinities. The flexibility of operation in either mode makes it especially attractive for RIB applications and, therefore, the source will be used as a complementary replacement for the high-temperature electron impact ionization sources presently in use at the HRIBF The design features and operational principles of the source will be described in this report

Novel product ions of 2-aminoanilide and benzimidazole Ag(I) complexes using electrospray ionization with multi-stage tandem mass spectrometry.

Science.gov (United States)

Johnson, Byron S; Burinsky, David J; Burova, Svetlana A; Davis, Roman; Fitzgerald, Russ N; Matsuoka, Richard T

2012-05-15

The 2-aminoaniline scaffold is of significant value to the pharmaceutical industry and is embedded in a number of pharmacophores including 2-aminoanilides and benzimidazoles. A novel application of coordination ion spray mass spectrometry (CIS-MS) for interrogating the silver ion (Ag(+)) complexes of a homologous series of these compounds using multi-stage tandem mass spectrometry is described. Unlike the ubiquitous alkali metal ion complexes, Ag(+) complexes of 2-aminoanilides and benzimidazoles were found to yield [M - H](+) ions in significant abundance via gas-phase elimination of the metal hydride (AgH) resulting in unique product ion cascades. Sample introduction was by liquid chromatography with mass spectrometry analysis performed on a hybrid linear ion trap/orbitrap instrument capable of high-resolution measurements. Rigorous structural characterization by multi-stage tandem mass spectrometry using [M +  H](+), [M - H](-) and [M - H](+) precursor ions derived from ESI and CIS experiments was performed for the homologous series of 2-aminoanilide and benzimidazole compounds. A full tabular comparison of structural information resulting from these product ion cascades was produced. Multi-stage tandem mass spectrometry of [M - H](+) ions resulting from Ag(+) complexes of 2-aminoanilides and benzimidazoles in CIS-MS experiments produced unique product ion cascades that exhibited complementary structural information to that obtained from tandem mass spectrometry of [M  +  H](+) and [M - H](-) ions by electrospray ionization (ESI). These observations may be broadly applicable to other compounds that are observed to form Ag(+) complexes and eliminate AgH. Copyright © 2012 John Wiley & Sons, Ltd.

Two competing ionization processes in ESI-MS analysis of N-(1,3-diphenylallyl)benzenamines: formation of the unusual [M-H]+ ion versus the regular [M+H]+ ion.

Science.gov (United States)

Fang, Liwen; Dong, Cheng; Guo, Cheng; Xu, Jianxing; Liu, Qiaoling; Qu, Zhirong; Jiang, Kezhi

2018-06-01

A series of N-(1,3-diphenylallyl)benzenamine derivatives (M) were investigated by electrospray ionization mass spectrometry in the positive-ion mode. Both the anomalous [M-H] + and the regular [M+H] + were observed in the ESI mass spectra. The occurrence of [M-H] + has been supported by accurate mass spectrometry, liquid chromatography mass spectrometry, and tandem mass spectrometry analysis. Calculation results indicated that formation of [M-H] + is attributed to the ion-molecule reaction of M with the protonated ESI solvent molecule (e.g. CH 3 OH 2 + ) via hydride abstraction from a tertiary C sp3 -H. The competing ionization processes leading to [M-H] + or [M+H] + were significantly affected by the concentration of formic acid in the electrospray ionization solvent and the proton affinity of the N atom.

Real-Time Metabolomics on Living Microorganisms Using Ambient Electrospray Ionization Flow-Probe

DEFF Research Database (Denmark)

Hsu, Cheng-Chih; ElNaggar, Mariam S.; Peng, Yao

2013-01-01

sampling probe for electrospray ionization-mass spectrometry to extract and ionize metabolite mixtures directly from living microbial colonies grown on soft nutrient agar in Petri-dishes without any sample pretreatment. To demonstrate the robustness of the method, this technique was applied to observe...

Improved detection of drugs of abuse using high-performance ion mobility spectrometry with electrospray ionization (ESI-HPIMS) for urine matrices.

Science.gov (United States)

Midey, Anthony J; Patel, Aesha; Moraff, Carol; Krueger, Clinton A; Wu, Ching

2013-11-15

High-performance ion mobility spectrometry (HPIMS) with electrospray ionization (ESI) has been used to separate drugs of abuse compounds as a function of drift time (ion mobility), which is based on their size, structural shape, and mass-to-charge. HPIMS has also been used to directly detect and identify a variety of the most commonly encountered illegal drugs, as well as a mixture of opiates in a urine matrix without extra sample pretreatment. HPIMS has shown resolving power greater than 65 comparable to that of high-performance liquid chromatography (HPLC) with only 1 mL of solvent and sample required using air as the IMS separation medium. The HPIMS method can achieve two-order of magnitude linear response, precise drift times, and high peak area precision with percent relative standard deviations (%RSD) less than 3% for sample quantitation. The reduced mobilities measured agree very well with other IMS measurements, allowing a simple "dilute-and-shoot" method to be used to detect a mixture of codeine and morphine in urine matrix. Copyright © 2013 Elsevier B.V. All rights reserved.

Beyond Naphthenic Acids: Environmental Screening of Water from Natural Sources and the Athabasca Oil Sands Industry Using Atmospheric Pressure Photoionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

Science.gov (United States)

Barrow, Mark P; Peru, Kerry M; Fahlman, Brian; Hewitt, L Mark; Frank, Richard A; Headley, John V

2015-09-01

There is a growing need for environmental screening of natural waters in the Athabasca region of Alberta, Canada, particularly in the differentiation between anthropogenic and naturally-derived organic compounds associated with weathered bitumen deposits. Previous research has focused primarily upon characterization of naphthenic acids in water samples by negative-ion electrospray ionization methods. Atmospheric pressure photoionization is a much less widely used ionization method, but one that affords the possibility of observing low polarity compounds that cannot be readily observed by electrospray ionization. This study describes the first usage of atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (in both positive-ion and negative-ion modes) to characterize and compare extracts of oil sands process water, river water, and groundwater samples from areas associated with oil sands mining activities. When comparing mass spectra previously obtained by electrospray ionization and data acquired by atmospheric pressure photoionization, there can be a doubling of the number of components detected. In addition to polar compounds that have previously been observed, low-polarity, sulfur-containing compounds and hydrocarbons that do not incorporate a heteroatom were detected. These latter components, which are not amenable to electrospray ionization, have potential for screening efforts within monitoring programs of the oil sands.

Toward single-cell analysis by plume collimation in laser ablation electrospray ionization mass spectrometry.

Science.gov (United States)

Stolee, Jessica A; Vertes, Akos

2013-04-02

Ambient ionization methods for mass spectrometry have enabled the in situ and in vivo analysis of biological tissues and cells. When an etched optical fiber is used to deliver laser energy to a sample in laser ablation electrospray ionization (LAESI) mass spectrometry, the analysis of large single cells becomes possible. However, because in this arrangement the ablation plume expands in three dimensions, only a small portion of it is ionized by the electrospray. Here we show that sample ablation within a capillary helps to confine the radial expansion of the plume. Plume collimation, due to the altered expansion dynamics, leads to greater interaction with the electrospray plume resulting in increased ionization efficiency, reduced limit of detection (by a factor of ~13, reaching 600 amol for verapamil), and extended dynamic range (6 orders of magnitude) compared to conventional LAESI. This enhanced sensitivity enables the analysis of a range of metabolites from small cell populations and single cells in the ambient environment. This technique has the potential to be integrated with flow cytometry for high-throughput metabolite analysis of sorted cells.

Soft Supercharging of Biomolecular Ions in Electrospray Ionization Mass Spectrometry

Science.gov (United States)

Chingin, Konstantin; Xu, Ning; Chen, Huanwen

2014-06-01

The charge states of biomolecular ions in ESI-MS can be significantly increased by the addition of low-vapor supercharging (SC) reagents into the spraying solution. Despite the considerable interest from the community, the mechanistic aspects of SC are not well understood and are hotly debated. Arguments that denaturation accounts for the increased charging observed in proteins sprayed from aqueous solutions containing SC reagent have been published widely, but often with incomplete or ambiguous supporting data. In this work, we explored ESI MS charging and SC behavior of several biopolymers including proteins and DNA oligonucleotides. Analytes were ionized from 100 mM ammonium acetate (NH4Ac) aqueous buffer in both positive (ESI+) and negative (ESI-) ion modes. SC was induced either with m-NBA or by the elevated temperature of ESI capillary. For all the analytes studied we, found striking differences in the ESI MS response to these two modes of activation. The data suggest that activation with m-NBA results in more extensive analyte charging with lower degree of denaturation. When working solution with m-NBA was analyzed at elevated temperatures, the SC effect from m-NBA was neutralized. Instead, the net SC effect was similar to the SC effect achieved by thermal activation only. Overall, our observations indicate that SC reagents enhance ESI charging of biomolecules via distinctly different mechanism compared with the traditional approaches based on analyte denaturation. Instead, the data support the hypothesis that the SC phenomenon involves a direct interaction between a biopolymer and SC reagent occurring in evaporating ESI droplets.

Ultra high performance liquid chromatography coupled with electrospray ionization/quadrupole time-of-flight mass spectrometry for the rapid analysis of constituents in the traditional Chinese medicine formula Wu Ji Bai Feng Pill.

Science.gov (United States)

Duan, Shengnan; Qi, Wen; Zhang, Siwen; Huang, Kunkun; Yuan, Dan

2017-10-01

An ultra high performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight mass spectrometry method in both positive and negative ion modes was established in order to comprehensively investigate the major constituents in Wu Ji Bai Feng Pill. Briefly, a Waters ACQUITY UPLC HSS C 18 column was used to separate the aqueous extract of Wu Ji Bai Feng Pill. A total of 0.1% formic acid in acetonitrile and 0.1% aqueous formic acid v/v were used as the mobile phase. All analytes were determined using quadrupole time-of-flight mass spectrometry with electrospray ionization source in positive and negative ion modes. At length, a total of 173 components including flavones and their glycosides, monoterpene glycosides, triterpene saponins, phenethylalchohol glycosides, iridoid glycosides, phthalides, tanshinones, phenolic acids, sesquiterpenoids and cyclopeptides were identified or tentatively characterized in Wu Ji Bai Feng Pill in an analysis of 16.0 min based on the accurate mass and tandem mass spectrometry behaviors. The developed method is rapid and highly sensitive to characterize the chemical constituents of Wu Ji Bai Feng Pill, which could not only be used for chemical standardization and quality control of Wu Ji Bai Feng Pill, but also be helpful for further study in vivo metabolism of Wu Ji Bai Feng Pill. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Desorption electro-spray ionization - orbitrap mass spectrometry of synthetic polymers and copolymers

International Nuclear Information System (INIS)

Friia, Manel; Legros, Veronique; Tortajada, Jeanine; Buchmann, William

2012-01-01

Desorption Electro-Spray Ionization (DESI) - Orbitrap Mass Spectrometry (MS) was evaluated as a new tool for the characterization of various industrial synthetic polymers (poly(ethylene glycol), poly(propylene glycol), poly(methylmethacrylate), poly(dimethylsiloxane)) and copolymers, with masses ranging from 500 g.mol -1 up to more than 20000 g.mol -1 . Satisfying results in terms of signal stability and sensitivity were obtained from hydrophobic surfaces (HTC Prosolia) with a mixture water/methanol (10/90) as spray solvent in the presence of sodium salt. Taking into account the formation of multiplied charged species by DESI-MS, a strategy based on the use of a deconvolution software followed by the automatic assignment of the ions was described allowing the rapid determination of Mn, Mw and PDI values. DESI-Orbitrap MS results were compared to those obtained from matrix-assisted laser desorption/ionization- time-of-flight MS and gel permeation chromatography. An application of DESI-Orbitrap MS for the detection and identification of polymers directly from cosmetics was described. (authors)

Liquid Chromatography with Post-Column Reagent Addition of Ammonia in Methanol Coupled to Negative Ion Electrospray Ionization Tandem Mass Spectrometry for Determination of Phenoxyacid Herbicides and their Degradation Products in Surface Water

Directory of Open Access Journals (Sweden)

Michele L. Etter

2010-02-01

Full Text Available A new liquid chromatography (LC-negative ion electrospray ionization (ESI–tandem mass spectrometry (MS/MS method with post-column addition of ammonia in methanol has been developed for the analysis of acid herbicides: 2,4-dichlorophenoxy ace- tic acid, 4-chloro-o-tolyloxyacetic acid, 2-(2-methyl-4-chlorophenoxybutyric acid, mecoprop, dichlorprop, 4-(2,4-dichlorophenoxy butyric acid, 2,4,5-trichlorophenoxy propionic acid, dicamba and bromoxynil, along with their degradation products: 4-chloro-2- methylphenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and 3,5-dibromo-4-hydroxybenzoic acid. The samples were extracted from the surface water matrix using solid-phase extraction (SPE with a polymeric sorbent and analyzed with LC ESI- with selected reaction monitoring (SRM using a three-point confirmation approach. Chromatography was performed on a Zorbax Eclipse XDB-C18 (50 × 4.6 mm i.d., 1.8 µm with a gradient elution using water-methanol with 2 mM ammonium acetate mobile phase at a flow rate of 0.15 mL/min. Ammonia in methanol (0.8 M was added post-column at a flow rate of 0.05 mL/min to enhance ionization of the deg- radation products in the MS source. One SRM transition was used for quantitative analysis while the second SRM along with the ratio of SRM1/SRM2 within the relative standard deviation determined by standards for each individual pesticide and retention time match were used for confirmation. The standard deviation of ratio of SRM1/SRM2 obtained from standards run on the day of analysis for different phenoxyacid herbicides ranged from 3.9 to 18.5%. Limits of detection (LOD were between 1 and 15 ng L-1 and method detection limits (MDL with strict criteria requiring

Super-atmospheric pressure ionization mass spectrometry and its application to ultrafast online protein digestion analysis.

Science.gov (United States)

Chen, Lee Chuin; Ninomiya, Satoshi; Hiraoka, Kenzo

2016-06-01

Ion source pressure plays a significant role in the process of ionization and the subsequent ion transmission inside a mass spectrometer. Pressurizing the ion source to a gas pressure greater than atmospheric pressure is a relatively new approach that aims to further improve the performance of atmospheric pressure ionization sources. For example, under a super-atmospheric pressure environment, a stable electrospray can be sustained for liquid with high surface tension such as pure water, because of the suppression of electric discharge. Even for nano-electrospray ionization (nano-ESI), which is known to work with aqueous solution, its stability and sensitivity can also be enhanced, particularly in the negative mode when the ion source is pressurized. A brief review on the development of super-atmospheric pressure ion sources, including high-pressure electrospray, field desorption and superheated ESI, and the strategies to interface these ion sources to a mass spectrometer will be given. Using a recent ESI prototype with an operating temperature at 220 °C under 27 atm, we also demonstrate that it is possible to achieve an online Asp-specific protein digestion analysis in which the whole processes of digestion, ionization and MS acquisition could be completed on the order of a few seconds. This method is fast, and the reaction can even be monitored on a near-real-time basis. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Determination of clebopride in plasma by capillary gas chromatography-negative-ion chemical ionization mass spectrometry.

Science.gov (United States)

Robinson, P R; Jones, M D; Maddock, J

1988-11-18

A procedure for the analysis of clebopride in plasma using capillary gas chromatography-negative-ion chemical ionization mass spectrometry has been developed. Employing an ethoxy analogue as internal standard, the two compounds were extracted from basified plasma using dichloromethane. Subsequent reaction with heptafluorobutyryl imidazole produced volatile monoheptafluorobutyryl derivatives whose ammonia negative-ion mass spectra proved ideal for selected-ion monitoring. The recovery of clebopride from plasma at 0.536 nmol/l was found to be 85.5 +/- 0.9% (n = 3) whilst measurement down to 0.268 nmol/l was possible with a coefficient of variation of 7.9%. Plasma levels of the compound are reported in two volunteers following ingestion of 1 mg of clebopride as the malate salt.

Gas-phase complexes formed between amidoxime ligands and vanadium or iron investigated using electrospray ionization mass spectrometry.

Science.gov (United States)

Mustapha, Adetayo M; Pasilis, Sofie P

2016-08-15

Amidoxime-functionalized sorbents can be used to extract uranium from seawater. Iron(III) and vanadium(V) may compete with uranium for adsorption sites. We use 2,6-dihydroxyiminopiperidine (DHIP) and N(1) ,N(5) -dihydroxypentanediimidamide (DHPD) to model amidoxime functional groups and characterize the vanadium(V) and iron(III) complexes with these ligands. We also examine the effect of iron(III) and vanadium(V) on uranyl(VI) complexation by DHIP and DHPD. The experiments were carried out in positive ion mode using a quadrupole ion trap mass spectrometer equipped with an electrospray ionization source. The effect on the mass spectra of changes in ligand, metal:ligand mole ratio, and pH was examined. Iron(III) formed a 1:2 metal:ligand complex with DHIP at all metal:ligand mole ratios and pH values investigated; it formed both 1:2 and 1:3 metal:ligand complexes with DHPD. Vanadium(V) formed 1:1 and 1:2 metal:ligand complexes with DHIP. A 1:2 metal:ligand complex was formed with DHPD at all vanadium(V):DHPD mole ratios investigated. Changes in solution pH did not affect the ions observed. The relative binding affinities of the metal ions towards DHIP followed the order iron(III) > vanadium(V) > uranyl(VI). This study presents a first look at the gas-phase vanadium(V)- and iron(III)-DHIP and -DHPD complexes using electrospray ionization mass spectrometry. These metals form stronger complexes with amidoxime ligands than uranyl(VI), and will affect uranyl(VI) adsorption to amidoxime-based sorbents. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Characterization of Proanthocyanidins from Parkia biglobosa (Jacq. G. Don. (Fabaceae by Flow Injection Analysis — Electrospray Ionization Ion Trap Tandem Mass Spectrometry and Liquid Chromatography/Electrospray Ionization Mass Spectrometry

Directory of Open Access Journals (Sweden)

Wagner Vilegas

2013-03-01

Full Text Available The present study investigates the chemical composition of the African plant Parkia biglobosa (Fabaceae roots and barks by Liquid Chromatography - Electrospray Ionization and Direct Injection Tandem Mass Spectrometry analysis. Mass spectral data indicated that B-type oligomers are present, namely procyanidins and prodelphinidins, with their gallate and glucuronide derivatives, some of them in different isomeric forms. The analysis evidenced the presence of up to 40 proanthocyanidins, some of which are reported for the first time. In this study, the antiradical activity of extracts of roots and barks from Parkia biglobosa was evaluated using DPPH method and they showed satisfactory activities.

Mass measurements of neutron-rich strontium and rubidium isotopes in the region $A \\approx 100$ and development of an electrospray ionization ion source

CERN Document Server

de Roubin, Antoine

An extension of the atomic mass surface in the region $A \\approx 100$ is performed via mass measurements of the $^{100−102}$Sr and $^{100−102}$Rb isotopes with the ion-trap mass spectrometer ISOLTRAP at CERN-ISOLDE. The first direct mass measurements of $^{102}$Sr and $^{101,102}$Rb are reported here. These measurements confirm the continuation of the region of nuclear deformation with the increase of neutron number, at least as far as $N = 65$. In order to interpret the deformation in the strontium isotopic chain and to determine whether an onset of deformation is present in heavier krypton isotopes, a comparison is made between experimental values and theoretical calculations available in the literature. To complete this comparison, Hartree-Fock-Bogoliubov calculations for even and odd isotopes are also presented, illustrating the competition of nuclear shapes in the region. The development of an electrospray ionization ion source is presented. This source can deliver a large range of isobaric masses ...

Direct analysis of triterpenes from high-salt fermented cucumbers using infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI)

Science.gov (United States)

High-salt samples present a challenge to mass spectrometry (MS) analysis, particularly when electrospray ionization (ESI) is used, requiring extensive sample preparation steps such as desalting, extraction, and purification. In this study, infrared matrix-assisted laser desorption electrospray ioniz...

Shrinking droplets in electrospray ionization and their influence on chemical equilibria.

Science.gov (United States)

Wortmann, Arno; Kistler-Momotova, Anna; Zenobi, Renato; Heine, Martin C; Wilhelm, Oliver; Pratsinis, Sotiris E

2007-03-01

We investigated how chemical equilibria are affected by the electrospray process, using simultaneous in situ measurements by laser-induced fluorescence (LIF) and phase Doppler anemometry (PDA). The motivation for this study was the increasing number of publications in which electrospray ionization mass spectrometry is used for binding constant determination. The PDA was used to monitor droplet size and velocity, whereas LIF was used to monitor fluorescent analytes within the electrospray droplets. Using acetonitrile as solvent, we found an average initial droplet diameter of 10 microm in the electrospray. The PDA allowed us to follow the evolution of these droplets down to a size of 1 microm. Rhodamine B-sulfonylchloride was used as a fluorescent analyte within the electrospray. By spatially resolved LIF it was possible to probe the dimerization equilibrium of this dye. Measurements at different spray positions showed no influence of the decreasing droplet size on the monomer-dimer equilibrium. However, with the fluorescent dye pair DCM and oxazine 1 it was shown that a concentration increase does occur within electrosprayed droplets, using fluorescence resonance energy transfer as a probe for the average pair distance.

Antioxidant activity and ultra-performance LC-electrospray ionization-quadrupole time-of-flight mass spectrometry for phenolics-based fingerprinting of Rose species: Rosa damascena, Rosa bourboniana and Rosa brunonii.

Science.gov (United States)

Kumar, Neeraj; Bhandari, Pamita; Singh, Bikram; Bari, Shamsher S

2009-02-01

Roses are one of the most important groups of ornamental plants and their fruits and flowers are used in a wide variety of food, nutritional products and different traditional medicines. The antioxidant activity of methanolic extracts from fresh flowers of three rose species (Rosa damascena, Rosa bourboniana and Rosa brunonii) was evaluated by 1,1-diphenyl-2-picryl hydrazyl (DPPH) free-radical method. The ability to scavenge DPPH radical was measured by the discoloration of the solution. The methanolic extract from R. brunonii exhibited maximum free-radical-scavenging activity (64.5+/-0.38%) followed by R. bourboniana (51.8+/-0.46%) and R. damascena (43.6+/-0.25%) at 100 microg/ml. Simultaneously, ultra-performance liquid chromatography coupled with electrospray ionization-quadrupole time-of-flight mass spectrometry (UPLC-ESI-QTOF-MS) was used to study phenolic composition in the methanolic extracts from the fresh flowers of rose species. The phenolic constituents were further investigated by direct infusion-ESI-QTOF-MS/MS in negative ion mode. Characteristic Electrospray ionization tandem mass spectrometry (ESI-MS/MS) spectra with other diagnostic fragment ions generated by retro Diels-Alder (RDA) fragmentation pathways were recorded for the flavonoids. Distinct similarities were observed in the relative distribution of polyphenolic compounds among the three species. The dominance of quercetin, kaempferol and their glycosides was observed in all the three species.

Virtual quantification of metabolites by capillary electrophoresis-electrospray ionization-mass spectrometry: predicting ionization efficiency without chemical standards.

Science.gov (United States)

Chalcraft, Kenneth R; Lee, Richard; Mills, Casandra; Britz-McKibbin, Philip

2009-04-01

A major obstacle in metabolomics remains the identification and quantification of a large fraction of unknown metabolites in complex biological samples when purified standards are unavailable. Herein we introduce a multivariate strategy for de novo quantification of cationic/zwitterionic metabolites using capillary electrophoresis-electrospray ionization-mass spectrometry (CE-ESI-MS) based on fundamental molecular, thermodynamic, and electrokinetic properties of an ion. Multivariate calibration was used to derive a quantitative relationship between the measured relative response factor (RRF) of polar metabolites with respect to four physicochemical properties associated with ion evaporation in ESI-MS, namely, molecular volume (MV), octanol-water distribution coefficient (log D), absolute mobility (mu(o)), and effective charge (z(eff)). Our studies revealed that a limited set of intrinsic solute properties can be used to predict the RRF of various classes of metabolites (e.g., amino acids, amines, peptides, acylcarnitines, nucleosides, etc.) with reasonable accuracy and robustness provided that an appropriate training set is validated and ion responses are normalized to an internal standard(s). The applicability of the multivariate model to quantify micromolar levels of metabolites spiked in red blood cell (RBC) lysates was also examined by CE-ESI-MS without significant matrix effects caused by involatile salts and/or major co-ion interferences. This work demonstrates the feasibility for virtual quantification of low-abundance metabolites and their isomers in real-world samples using physicochemical properties estimated by computer modeling, while providing deeper insight into the wide disparity of solute responses in ESI-MS. New strategies for predicting ionization efficiency in silico allow for rapid and semiquantitative analysis of newly discovered biomarkers and/or drug metabolites in metabolomics research when chemical standards do not exist.

Comparison of the sensitivity of mass spectrometry atmospheric pressure ionization techniques in the analysis of porphyrinoids.

Science.gov (United States)

Swider, Paweł; Lewtak, Jan P; Gryko, Daniel T; Danikiewicz, Witold

2013-10-01

The porphyrinoids chemistry is greatly dependent on the data obtained in mass spectrometry. For this reason, it is essential to determine the range of applicability of mass spectrometry ionization methods. In this study, the sensitivity of three different atmospheric pressure ionization techniques, electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization, was tested for several porphyrinods and their metallocomplexes. Electrospray ionization method was shown to be the best ionization technique because of its high sensitivity for derivatives of cyanocobalamin, free-base corroles and porphyrins. In the case of metallocorroles and metalloporphyrins, atmospheric pressure photoionization with dopant proved to be the most sensitive ionization method. It was also shown that for relatively acidic compounds, particularly for corroles, the negative ion mode provides better sensitivity than the positive ion mode. The results supply a lot of relevant information on the methodology of porphyrinoids analysis carried out by mass spectrometry. The information can be useful in designing future MS or liquid chromatography-MS experiments. Copyright © 2013 John Wiley & Sons, Ltd.

High throughput reaction screening using desorption electrospray ionization mass spectrometry.

Science.gov (United States)

Wleklinski, Michael; Loren, Bradley P; Ferreira, Christina R; Jaman, Zinia; Avramova, Larisa; Sobreira, Tiago J P; Thompson, David H; Cooks, R Graham

2018-02-14

We report the high throughput analysis of reaction mixture arrays using methods and data handling routines that were originally developed for biological tissue imaging. Desorption electrospray ionization (DESI) mass spectrometry (MS) is applied in a continuous on-line process at rates that approach 10 4 reactions per h at area densities of up to 1 spot per mm 2 (6144 spots per standard microtiter plate) with the sprayer moving at ca. 10 4 microns per s. Data are analyzed automatically by MS using in-house software to create ion images of selected reagents and products as intensity plots in standard array format. Amine alkylation reactions were used to optimize the system performance on PTFE membrane substrates using methanol as the DESI spray/analysis solvent. Reaction times can be screening of processes like N -alkylation and Suzuki coupling reactions as reported herein. Products and by-products were confirmed by on-line MS/MS upon rescanning of the array.

Quantification of cardiolipin by liquid chromatography-electrospray ionization mass spectrometry.

Science.gov (United States)

Garrett, Teresa A; Kordestani, Reza; Raetz, Christian R H

2007-01-01

Cardiolipin (CL), a tetra-acylated glycerophospholipid composed of two phosphatidyl moieties linked by a bridging glycerol, plays an important role in mitochondrial function in eukaryotic cells. Alterations to the content and acylation state of CL cause mitochondrial dysfunction and may be associated with pathologies such as ischemia, hypothyrodism, aging, and heart failure. The structure of CL is very complex because of microheterogeneity among its four acyl chains. Here we have developed a method for the quantification of CL molecular species by liquid chromatography-electrospray ionization mass spectrometry. We quantify the [M-2H](2-) ion of a CL of a given molecular formula and identify the CLs by their total number of carbons and unsaturations in the acyl chains. This method, developed using mouse macrophage RAW 264.7 tumor cells, is broadly applicable to other cell lines, tissues, bacteria and yeast. Furthermore, this method could be used for the quantification of lyso-CLs and bis-lyso-CLs.

Structural analysis and differentiation of reducing and nonreducing neutral model starch oligosaccharides by negative-ion electrospray ionization ion-trap mass spectrometry

Czech Academy of Sciences Publication Activity Database

Čmelík, Richard; Chmelík, Josef

2010-01-01

Roč. 291, 1-2 (2010), s. 33-40 ISSN 1387-3806 R&D Projects: GA MŠk 2B06037 Institutional research plan: CEZ:AV0Z40310501 Keywords : structural analysis * oligosaccharides * electrospray mass spectrometry Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.009, year: 2010

Derivatization reagents in liquid chromatography/electrospray ionization tandem mass spectrometry.

Science.gov (United States)

Santa, Tomofumi

2011-01-01

Liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) is one of the most prominent analytical techniques owing to its inherent selectivity and sensitivity. In LC/ESI-MS/MS, chemical derivatization is often used to enhance the detection sensitivity. Derivatization improves the chromatographic separation, and enhances the mass spectrometric ionization efficiency and MS/MS detectability. In this review, an overview of the derivatization reagents which have been applied to LC/ESI-MS/MS is presented, focusing on the applications to low molecular weight compounds. 2010 John Wiley & Sons, Ltd.

Fate and behavior of oil sands naphthenic acids in a pilot-scale treatment wetland as characterized by negative-ion electrospray ionization Orbitrap mass spectrometry.

Science.gov (United States)

Ajaero, Chukwuemeka; Peru, Kerry M; Simair, Monique; Friesen, Vanessa; O'Sullivan, Gwen; Hughes, Sarah A; McMartin, Dena W; Headley, John V

2018-08-01

Large volumes of oil sands process-affected water (OSPW) are generated during the extraction of bitumen from oil sands in the Athabasca region of northeastern Alberta, Canada. As part of the development of treatment technologies, molecular characterization of naphthenic acids (NAs) and naphthenic acid fraction compounds (NAFC) in wetlands is a topic of research to better understand their fate and behavior in aquatic environments. Reported here is the application of high-resolution negative-ion electrospray Orbitrap-mass spectrometry for molecular characterization of NAs and NAFCs in a non-aerated constructed treatment wetland. The effectiveness of the wetlands to remove OSPW-NAs and NAFCs was evaluated by monitoring the changes in distributions of NAFC compounds in the untreated sample and non-aerated treatment system. After correction for measured evapotranspiration, the removal rate of the classical NAs followed approximately first-order kinetics, with higher rates observed for structures with relatively higher number of carbon atoms. These findings indicate that constructed wetland treatment is a viable method for removal of classical NAs in OSPW. Work is underway to evaluate the effects of wetland design on water quality improvement, preferential removal of different NAFC species, and reduction in toxicity. Copyright © 2018. Published by Elsevier B.V.

Analysis of metals in solution using electrospray ionization mass spectrometry

International Nuclear Information System (INIS)

Van Berkel, G.J.; McLuckey, S.A.; Glish, G.L.

1991-01-01

Electrospray ionization-mass spectrometry (ES-MS) has gained most of its recent attention because of the ability to produce multiply charged ions from very large biomolecules making them amenable to analysis by most modern mass spectrometers. However, ES-MS is equally well suited for compounds of low or moderate molecular weight that are difficult to volatilize intact by others methods. Moreover, the early work of Fenn and co-workers (1,2) and recent reports by Kebarle and co-workers (3,4) attest to the applicability of ES-MS to the study of the gas-phase chemistry of multiply solvated or coordinated metal ions. The utility of ES-MS for the analysis of metals in solution derives in part from the facility with which the metal ions are solvated by or form complexes with the ES solvent or other reagents added to the solvent. Solvation and complexation can be a hindrance, however, in the analytical application of ES-MS to the analysis of metals in solution, especially solutions of metals in water. The data presented here demonstrate that many of the problems in the ES-MS analysis of metals can be overcome by complexing the metals with crown ethers and/or extracting the metals from water into an organic phase using crown ethers. 5 refs., 4 figs

Hydrophilic interaction liquid chromatography/positive ion electrospray ionization mass spectrometry method for the quantification of alprazolam and α-hydroxy-alprazolam in human plasma.

Science.gov (United States)

Kalogria, Eleni; Pistos, Constantinos; Panderi, Irene

2013-12-30

A hydrophilic interaction liquid chromatography/positive ion electrospray-mass spectrometry (HILIC-ESI/MS) has been developed and fully validated for the quantification of alprazolam and its main metabolite, α-hydroxy-alprazolam, in human plasma. The assay is based on 50μL plasma samples, following liquid-liquid extraction. All analytes and the internal standard (tiamulin) were separated by hydrophilic interaction liquid chromatography using an X-Bridge-HILIC analytical column (150.0mm×2.1mm i.d., particle size 3.5μm) under isoscratic elution. The mobile phase was composed of a 7% 10mM ammonium formate water solution in acetonitrile and pumped at a flow rate of 0.20mLmin(-1). Running in positive electrospray ionization and selected ion monitoring (SIM) the mass spectrometer was set to analyze the protonated molecules [M+H](+) at m/z 309, 325 and 494 for alprazolam, α-hydroxy-alprazolam and tiamulin (ISTD) respectively. The assay was linear over the concentration range of 2.5-250ngmL(-1) for alprazolam and 2.5-50ngmL(-1) for α-hydroxy alprazolam. Intermediate precision was less than 4.1% over the tested concentration ranges. The method is the first reported application of HILIC in the analysis benzodiazepines in human plasma. With a small sample size (50μL human plasma) and a run time less than 10.0min for each sample the method can be used to support a wide range of clinical studies concerning alprazolam quantification. Copyright © 2013 Elsevier B.V. All rights reserved.

Identification of ionic chloroacetanilide-herbicide metabolites in surface water and groundwater by HPLC/MS using negative ion spray

Science.gov (United States)

Ferrer, I.; Thurman, E.M.; Barcelo, D.

1997-01-01

Solid-phase extraction (SPE) was combined with high-performance liquid chromatography/high-flow pneumatically assisted electrospray mass spectrometry (HPLC/ESP/MS) for the trace analysis of oxanilic and sulfonic acids of acetochlor, alachlor, and metolachlor. The isolation procedure separated the chloroacetanilide metabolites from the parent herbicides during the elution from C18 cartridges using ethyl acetate for parent compounds, followed by methanol for the anionic metabolites. The metabolites were separated chromatographically using reversed-phase HPLC and analyzed by negative-ion MS using electrospray ionization in selected ion mode. Quantitation limits were 0.01 ??g/L for both the oxanilic and sulfonic acids based on a 100-mL water sample. This combination of methods represents an important advance in environmental analysis of chloroacetanilide-herbicide metabolites in surface water and groundwater for two reasons. First, anionic chloroacetanilide metabolites are a major class of degradation products that are readily leached to groundwater in agricultural areas. Second, anionic metabolites, which are not able to be analyzed by conventional methods such as liquid extraction and gas chromatography/mass spectrometry, are effectively analyzed by SPE and high-flow pneumatically assisted electrospray mass spectrometry. This paper reports the first HPLC/MS identification of these metabolites in surface water and groundwater.

Specificity enhancement by electrospray ionization multistage mass spectrometry--a valuable tool for differentiation and identification of 'V'-type chemical warfare agents.

Science.gov (United States)

Weissberg, Avi; Tzanani, Nitzan; Dagan, Shai

2013-12-01

The use of chemical warfare agents has become an issue of emerging concern. One of the challenges in analytical monitoring of the extremely toxic 'V'-type chemical weapons [O-alkyl S-(2-dialkylamino)ethyl alkylphosphonothiolates] is to distinguish and identify compounds of similar structure. MS analysis of these compounds reveals mostly fragment/product ions representing the amine-containing residue. Hence, isomers or derivatives with the same amine residue exhibit similar mass spectral patterns in both classical EI/MS and electrospray ionization-MS, leading to unavoidable ambiguity in the identification of the phosphonate moiety. A set of five 'V'-type agents, including O-ethyl S-(2-diisopropylamino)ethyl methylphosphonothiolate (VX), O-isobutyl S-(2-diethylamino)ethyl methylphosphonothiolate (RVX) and O-ethyl S-(2-diethylamino)ethyl methylphosphonothiolate (VM) were studied by liquid chromatography/electrospray ionization/MS, utilizing a QTRAP mass detector. MS/MS enhanced product ion scans and multistage MS(3) experiments were carried out. Based on the results, possible fragmentation pathways were proposed, and a method for the differentiation and identification of structural isomers and derivatives of 'V'-type chemical warfare agents was obtained. MS/MS enhanced product ion scans at various collision energies provided information-rich spectra, although many of the product ions obtained were at low abundance. Employing MS(3) experiments enhanced the selectivity for those low abundance product ions and provided spectra indicative of the different phosphonate groups. Study of the fragmentation pathways, revealing some less expected structures, was carried out and allowed the formulation of mechanistic rules and the determination of sets of ions typical of specific groups, for example, methylphosphonothiolates versus ethylphosphonothiolates. The new group-specific ions elucidated in this work are also useful for screening unknown 'V'-type agents and related

Electrospray ionization mass spectrometry for the hydrolysis complexes of cisplatin: implications for the hydrolysis process of platinum complexes.

Science.gov (United States)

Feifan, Xie; Pieter, Colin; Jan, Van Bocxlaer

2017-07-01

Non-enzyme-dependent hydrolysis of the drug cisplatin is important for its mode of action and toxicity. However, up until today, the hydrolysis process of cisplatin is still not completely understood. In the present study, the hydrolysis of cisplatin in an aqueous solution was systematically investigated by using electrospray ionization mass spectrometry coupled to liquid chromatography. A variety of previously unreported hydrolysis complexes corresponding to monomeric, dimeric and trimeric species were detected and identified. The characteristics of the Pt-containing complexes were investigated by using collision-induced dissociation (CID). The hydrolysis complexes demonstrate distinctive and correlative CID characteristics, which provides tools for an informative identification. The most frequently observed dissociation mechanism was sequential loss of NH 3 , H 2 O and HCl. Loss of the Pt atom was observed as the final step during the CID process. The formation mechanisms of the observed complexes were explored and experimentally examined. The strongly bound dimeric species, which existed in solution, are assumed to be formed from the clustering of the parent compound and its monohydrated or dihydrated complexes. The role of the electrospray process in the formation of some of the observed ions was also evaluated, and the electrospray ionization-related cold clusters were identified. The previously reported hydrolysis equilibria were tested and subsequently refined via a hydrolysis study resulting in a renewed mechanistic equilibrium system of cisplatin as proposed from our results. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Investigation of Uranyl Nitrate Ion Pairs Complexed with Amide Ligands using Electrospray Ionization Ion Trap Mass Spectrometry and Density Functional Theory

International Nuclear Information System (INIS)

Groenewold, Gary S.; Dinescu, Adriana; Benson, Michael T.; Gresham, Garold L.; van Stipdonk, Michael J.

2011-01-01

Ion populations formed from electrospray of uranyl nitrate solutions containing different amides vary depending on ligand nucleophilicity and steric crowding at the metal center. The most abundant species were ion pair complexes having the general formula (UO2(NO3)(amide)n=2,3)+, and complexes containing the amide conjugate base, reduced uranyl UO2+, and a 2+ charge were also formed. The formamide experiment produced the greatest diversity of species that stems from weaker amide binding leading to dissociation and subsequent solvent coordination or metal reduction. Experiments using methyl formamide, dimethyl formamide, acetamide, and methyl acetamide produced ion pair and doubly charged complexes that were more abundant, and less abundant complexes containing solvent or reduced uranyl. This pattern is reversed in the dimethylacetamide experiment, which displayed reduced doubly charged complexes and augmented reduced uranyl complexes. DFT investigations of the tris-amide ion pair complexes showed that inter-ligand repulsion distorts the amide ligands out of the uranyl equatorial plane, and that complex stabilities do not increase with increasing amide nucleophilicity. Elimination of an amide ligand largely relieves the interligand repulsion, and the remaining amide ligands become closely aligned with the equatorial plane in the structures of the bis-amide ligands. The studies show that the phenomenological distribution of coordination complexes in a metal-ligand electrospray experiment is a function of both ligand nucleophilicity and interligand repulsion, and that the latter factor begins exerting influence even in the case of relatively small ligands like the substituted methyl-formamide and methyl-acetamide ligands.

Explosives vapour identification in ion mobility spectrometry using a tunable laser ionization source: a comparison with conventional 63Ni ionization

International Nuclear Information System (INIS)

Clark, A.; Deas, R.M.; Kosmidis, C.; Ledingham, K.W.D.; Marshall, A.; Singhal, R.P.

1995-01-01

Laser multiphoton ionization (MPI) is used to produce ions from explosive vapours at atmospheric pressure in air for analysis by ion mobility spectrometry (IMS). In the positive ion mode of detection, NO + ions, generated directly by multiphoton dissociation/ionization of the explosive compounds, show strong variation with laser wavelength. This provides a means of identifying the presence of nitro-containing compounds. Moreover, electrons formed in the MPI of gaseous components in the air carrier stream, primarily O 2 , are transferred via neutral molecular oxygen (O 2 ) to trace explosive vapour, forming negative ions which give rise to characteristic and identifiable ion mobility spectra. Further, negative ion mobility spectra of several explosive vapours are presented using conventional 63 Ni ionization and are compared qualitatively with the laser ionization approach. (author)

Negative ion sourcery

International Nuclear Information System (INIS)

Os, C.F.A. van.

1989-01-01

The work described in this thesis is involved by current research programs in the field of nuclear-fusion. A brief introduction to fusion is given, anticipated problems related to current drive of the fusion plasma are pinpointed and probable suggestions to overcome these problems are described. One probable means for current drive is highlighted; Neutral Beam Injection (NBI). This is based on injecting a 1 MeV neutral hydrogen or deuterium beam into a fusion plasma. Negative ions are needed as primary particles because they can easily be neutralized at 1 MeV. The two current schemes for production of negative ions are described, volume production and negative surface ionization. The latter method is extensively studied in this thesis. (author). 171 refs.; 55 figs.; 7 tabs

Quantum effects on the formation of negative hydrogen ion by polarization electron capture in partially ionized dense hydrogen plasmas

International Nuclear Information System (INIS)

Jung, Young-Dae; Kato, Daiji

2009-05-01

The quantum effects on the formation of the negative hydrogen ion (H - ) by the polarization electron capture process are investigated in partially ionized dense hydrogen plasmas. It is shown that the quantum effect strongly suppresses the electron capture radius as well as the cross section for the formation of the negative hydrogen ion. In addition, it has been found that the electron capture position is receded from the center of the projectile with decreasing the quantum effect of the plasma. (author)

Regioisomers of octanoic acid-containing structured triacylglycerols analyzed by tandem mass spectrometry using ammonia negative ion chemical ionization

DEFF Research Database (Denmark)

Kurvinen, J.P.; Mu, Huiling; Kallio, H.

2001-01-01

Tandem mass spectrometry based on ammonia negative ion chemical ionization and sample introduction via direct exposure probe was applied to analysis of regioisomeric structures of octanoic acid containing structured triacylglycerols (TAG) of type MML, MLM, MLL, and LML (M, medium-chain fatty acid...

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

Science.gov (United States)

Harmon, Christopher W.; Mang, Stephen A.; Greaves, John; Finlayson-Pitts, Barbara J.

2010-01-01

Electrospray ionization mass spectrometry (ESI-MS) and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) have found increasing application in the analysis of biological samples. Using these techniques to solve problems in analytical chemistry should be an essential component of the training of undergraduate chemists. We…

Fischer Indole Synthesis in the Gas Phase, the Solution Phase, and at the Electrospray Droplet Interface.

Science.gov (United States)

Bain, Ryan M; Ayrton, Stephen T; Cooks, R Graham

2017-07-01

Previous reports have shown that reactions occurring in the microdroplets formed during electrospray ionization can, under the right conditions, exhibit significantly greater rates than the corresponding bulk solution-phase reactions. The observed acceleration under electrospray ionization could result from a solution-phase, a gas-phase, or an interfacial reaction. This study shows that a gas-phase ion/molecule (or ion/ion) reaction is not responsible for the observed rate enhancement in the particular case of the Fischer indole synthesis. The results show that the accelerated reaction proceeds in the microdroplets, and evidence is provided that an interfacial process is involved. Graphical Abstract GRAPHICAL ABSTRACT TEXT HERE] -->.

Electrospray Ionization with High-Resolution Mass Spectrometry as a Tool for Lignomics: Lignin Mass Spectrum Deconvolution

Science.gov (United States)

Andrianova, Anastasia A.; DiProspero, Thomas; Geib, Clayton; Smoliakova, Irina P.; Kozliak, Evguenii I.; Kubátová, Alena

2018-05-01

The capability to characterize lignin, lignocellulose, and their degradation products is essential for the development of new renewable feedstocks. Electrospray ionization high-resolution time-of-flight mass spectrometry (ESI-HR TOF-MS) method was developed expanding the lignomics toolkit while targeting the simultaneous detection of low and high molecular weight (MW) lignin species. The effect of a broad range of electrolytes and various ionization conditions on ion formation and ionization effectiveness was studied using a suite of mono-, di-, and triarene lignin model compounds as well as kraft alkali lignin. Contrary to the previous studies, the positive ionization mode was found to be more effective for methoxy-substituted arenes and polyphenols, i.e., species of a broadly varied MW structurally similar to the native lignin. For the first time, we report an effective formation of multiply charged species of lignin with the subsequent mass spectrum deconvolution in the presence of 100 mmol L-1 formic acid in the positive ESI mode. The developed method enabled the detection of lignin species with an MW between 150 and 9000 Da or higher, depending on the mass analyzer. The obtained M n and M w values of 1500 and 2500 Da, respectively, were in good agreement with those determined by gel permeation chromatography. Furthermore, the deconvoluted ESI mass spectrum was similar to that obtained with matrix-assisted laser desorption/ionization (MALDI)-HR TOF-MS, yet featuring a higher signal-to-noise ratio. The formation of multiply charged species was confirmed with ion mobility ESI-HR Q-TOF-MS. [Figure not available: see fulltext.

Characterization of Nα-Fmoc-protected dipeptide isomers by electrospray ionization tandem mass spectrometry (ESI-MS(n)): effect of protecting group on fragmentation of dipeptides.

Science.gov (United States)

Ramesh, M; Raju, B; Srinivas, R; Sureshbabu, V V; Vishwanatha, T M; Hemantha, H P

2011-07-30

A series of positional isomeric pairs of Fmoc-protected dipeptides, Fmoc-Gly-Xxx-OY/Fmoc-Xxx-Gly-OY (Xxx=Ala, Val, Leu, Phe) and Fmoc-Ala-Xxx-OY/Fmoc-Xxx-Ala-OY (Xxx=Leu, Phe) (Fmoc=[(9-fluorenylmethyl)oxy]carbonyl) and Y=CH(3)/H), have been characterized and differentiated by both positive and negative ion electrospray ionization ion-trap tandem mass spectrometry (ESI-IT-MS(n)). In contrast to the behavior of reported unprotected dipeptide isomers which mainly produce y(1)(+) and/or a(1)(+) ions, the protonated Fmoc-Xxx-Gly-OY, Fmoc-Ala-Xxx-OY and Fmoc-Xxx-Ala-OY yield significant b(1)(+) ions. These ions are formed, presumably with stable protonated aziridinone structures. However, the peptides with Gly- at the N-terminus do not form b(1)(+) ions. The [M+H](+) ions of all the peptides undergo a McLafferty-type rearrangement followed by loss of CO(2) to form [M+H-Fmoc+H](+). The MS(3) collision-induced dissociation (CID) of these ions helps distinguish the pairs of isomeric dipeptides studied in this work. Further, negative ion MS(3) CID has also been found to be useful for differentiating these isomeric peptide acids. The MS(3) of [M-H-Fmoc+H](-) of isomeric peptide acids produce c(1)(-), z(1)(-) and y(1)(-) ions. Thus the present study of Fmoc-protected peptides provides additional information on mass spectral characterization of the dipeptides and distinguishes the positional isomers. Copyright © 2011 John Wiley & Sons, Ltd.

Prototype inverted sputter source for negative heavy ions

International Nuclear Information System (INIS)

Minehara, Eisuke; Kobayashi, Chiaki; Kikuchi, Shiroh

1977-10-01

A sputter source from which negative heavy ion beam is extracted through a tungsten wire and disc ionizer was built and tested. An alkali metal surface ionization gun with the ionizer is described, and also performance of the surface ionization gun and of the sputter source for negative heavy ions using the gun is reported. The gun was tested for three alkali metals, i.e. sodium, potassium and cesium. Total potassium beam current of 1-2mA was obtained at entrance aperture of the magnet. Sputtering materials and gases for producing negative heavy ions are carbon, copper, aluminium, molybdenum, oxygen and air. With carbon and leakage air, the beam intensities analyzed are: 2-5μA (at Faraday cup) and 4.6-11μA (at exit slit) for C - , 3-5μA (at Faraday cup) and 6.8-11μA (at exit slit) for 2C - , and 11-15μA (at Faraday cup) and 25-34μA (at exit slit) for O - . Total beam current at the entrance aperture was 200-400μA. (auth.)

Evaporation and discharge dynamics of highly charged multicomponent droplets generated by electrospray ionization.

Science.gov (United States)

Grimm, Ronald L; Beauchamp, J L

2010-01-28

We investigate the Rayleigh discharge and evaporation dynamics of highly charged two-component droplets consisting principally of methanol with 2-methoxyethanol, tert-butanol, or m-nitrobenzyl alcohol. A phase Doppler anemometer (PDA) characterizes droplets generated by electrospray ionization (ESI) according to size, velocity, and charge as they move through a uniform electric field within an ion mobility spectrometer (IMS). Repeated field reversals result in droplet "ping-pong" through the PDA. This generates individual droplet histories of solvent evaporation behavior and the dynamics of charge loss to progeny droplets during Rayleigh discharge events. On average, methanol droplets discharge at 127% their Rayleigh limit of charge, q(R), and release 25% of the net charge. Charge loss from methanol/2-methoxyethanol droplets behaves similarly to pure 2-methoxyethanol droplets which release approximately 28% of their net charge. Binary methanol droplets containing up to 50% tert-butanol discharge at a lower percent q(R) than pure methanol and release a greater fraction of their net charge. Mixed 99% methanol/1% m-nitrobenzyl alcohol droplets possess discharge characteristics similar to those of methanol. However, droplets of methanol containing 2% m-nitrobenzyl evaporate down to a fixed size and charge that remains constant with no observable discharges. Quasi-steady-state evaporation models accurately describe observed evaporation phenomena in which methanol/tert-butanol droplets evaporate at a rate similar to that of pure methanol and methanol/2-methoxyethanol droplets evaporate at a rate similar to that of 2-methoxyethanol. We compare these results to previous Rayleigh discharge experiments and discuss the implications for binary solvents in electrospray mass spectrometry (ESI-MS) and field-induced droplet ionization mass spectrometry (FIDI-MS).

Soft ionization of saturated hydrocarbons, alcohols and nonpolar compounds by negative-ion direct analysis in real-time mass spectrometry.

Science.gov (United States)

Cody, Robert B; Dane, A John

2013-03-01

Large polarizable n-alkanes (approximately C18 and larger), alcohols, and other nonpolar compounds can be detected as negative ions when sample solutions are injected directly into the sampling orifice of the atmospheric pressure interface of the time-of-flight mass spectrometer with the direct analysis in real time (DART) ion source operating in negative-ion mode. The mass spectra are dominated by peaks corresponding to [M + O2]‾(•). No fragmentation is observed, making this a very soft ionization technique for samples that are otherwise difficult to analyze by DART. Detection limits for cholesterol were determined to be in the low nanogram range.

Characterization of microstructured fibre emitters: in pursuit of improved nano electrospray ionization performance.

Science.gov (United States)

Wu, Xinyun; Oleschuk, Richard D; Cann, Natalie M

2012-09-21

Full-dimensional computational fluid dynamics (CFD) simulations are presented for nano electrospray ionization (ESI) with various emitter designs. Our CFD electrohydrodynamic simulations are based on the Taylor-Melcher leaky-dielectric model, and the volume of fluid technique for tracking the fast-changing liquid-gas interface. The numerical method is first validated for a conventional 20 μm inner diameter capillary emitter. The impact of ESI voltage, flow rate, emitter tapering, surface hydrophobicity, and fluid conductivity on the nano-ESI behavior are thoroughly investigated and compared with experiments. Multi-electrospray is further simulated with 2-hole and 3-hole emitters with the latter having a linear or triangular hole arrangement. The simulations predict multi-electrospray behavior in good agreement with laboratory observations.

Electrosprayed Heavy Ion and Nanodrop Beams for Surface Engineering and Electrical Propulsion

Science.gov (United States)

2014-09-10

Studies At the macroscale, the surface of a Taylor cone just before ion emission is an equipotential with a normal electric field strength found from...AFRL-OSR-VA-TR-2014-0246 Electrosprayed Heavy Ion and Nanodrop Beams for Surface Engineering M Gamero-Castano UNIVERSITY OF CALIFORNIA IRVINE Final...298 (Re . 8-98) v Prescribed by ANSI Std. Z39.18 1 Electrosprayed Heavy Ion and Nanodrop Beams for Surface Engineering and Electrical Propulsion

Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry

Directory of Open Access Journals (Sweden)

K. E. Altieri

2009-04-01

Full Text Available Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS. Elemental compositions of 552 unique molecular species were determined in the mass range 50–500 Da in the rainwater. Four main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO only, sulfur (S containing CHOS compounds, nitrogen (N containing CHON compounds, and S- and N- containing CHONS compounds. Organic acids commonly identified in precipitation were detected in the rainwater. Within the four main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitrooxy-organosulfates were assigned based on elemental formula comparisons. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter.

Determination of Aspartame and Caffeine in Carbonated Beverages Utilizing Electrospray Ionization-Mass Spectrometry

Science.gov (United States)

Bergen, H. Robert, III; Benson, Linda M.; Naylor, Stephen

2000-10-01

Mass spectrometry has undergone considerable changes in the past decade. The advent of "soft ionization" techniques such as electrospray ionization (ESI) affords the direct analysis of very polar molecules without need for the complex inefficient derivatization procedures often required in GC-MS. These ionization techniques make possible the direct mass spectral analysis of polar nonvolatile molecules such as DNA and proteins, which previously were difficult or impossible to analyze by MS. Compounds that readily take on a charge (acids and bases) lend themselves to ESI-MS analysis, whereas compounds that do not readily accept a charge (e.g. sugars) are often not seen or are seen only as inefficient adducts (e.g., M+Na+). To gain exposure to this state-of-the-art analytical procedure, high school students utilize ESI-MS in an analysis of aspartame and caffeine. They dilute a beverage sample and inject the diluted sample into the ESI-MS. The lab is procedurally simple and the results clearly demonstrate the potential and limitations of ESI-coupled mass spectrometry. Depending upon the instructional goals, the outlined procedures can be used to quantify the content of caffeine and aspartame in beverages or to understand the capabilities of electrospray ionization.

A Comparison of Tissue Spray and Lipid Extract Direct Injection Electrospray Ionization Mass Spectrometry for the Differentiation of Eutopic and Ectopic Endometrial Tissues

Science.gov (United States)

Chagovets, Vitaliy; Wang, Zhihao; Kononikhin, Alexey; Starodubtseva, Natalia; Borisova, Anna; Salimova, Dinara; Popov, Igor; Kozachenko, Andrey; Chingin, Konstantin; Chen, Huanwen; Frankevich, Vladimir; Adamyan, Leila; Sukhikh, Gennady

2018-02-01

Recent research revealed that tissue spray mass spectrometry enables rapid molecular profiling of biological tissues, which is of great importance for the search of disease biomarkers as well as for online surgery control. However, the payback for the high speed of analysis in tissue spray analysis is the generally lower chemical sensitivity compared with the traditional approach based on the offline chemical extraction and electrospray ionization mass spectrometry detection. In this study, high resolution mass spectrometry analysis of endometrium tissues of different localizations obtained using direct tissue spray mass spectrometry in positive ion mode is compared with the results of electrospray ionization analysis of lipid extracts. Identified features in both cases belong to three lipid classes: phosphatidylcholines, phosphoethanolamines, and sphingomyelins. Lipids coverage is validated by hydrophilic interaction liquid chromatography with mass spectrometry of lipid extracts. Multivariate analysis of data from both methods reveals satisfactory differentiation of eutopic and ectopic endometrium tissues. Overall, our results indicate that the chemical information provided by tissue spray ionization is sufficient to allow differentiation of endometrial tissues by localization with similar reliability but higher speed than in the traditional approach relying on offline extraction.

Evaluation of Negative-Ion-Beam Driver Concepts for Heavy Ion Fusion

International Nuclear Information System (INIS)

Grisham, Larry R.

2002-01-01

We evaluate the feasibility of producing and using atomically neutral heavy ion beams produced from negative ions as drivers for an inertial confinement fusion reactor. Bromine and iodine appear to be the most attractive elements for the driver beams. Fluorine and chlorine appear to be the most appropriate feedstocks for initial tests of extractable negative ion current densities. With regards to ion sources, photodetachment neutralizers, and vacuum requirements for accelerators and beam transport, this approach appears feasible within existing technology, and the vacuum requirements are essentially identical to those for positive ion drivers except in the target chamber. The principal constraint is that this approach requires harder vacuums in the target chamber than do space-charge-neutralized positive ion drivers. With realistic (but perhaps pessimistic) estimates of the total ionization cross section, limiting the ionization of a neutral beam to less than 5% while traversing a four -meter path would require a chamber pressure of no more than 5 x 10 -5 torr. Alternatively, even at chamber pressures that are too high to allow propagation of atomically neutral beams, the negative ion approach may still have appeal, since it precludes the possibly serious problem of electron contamination of a positive ion beam during acceleration, drift compression, and focusing

Negative ion formation processes: A general review

International Nuclear Information System (INIS)

Alton, G.D.

1990-01-01

The principal negative ion formation processes will be briefly reviewed. Primary emphasis will be placed on the more efficient and universal processes of charge transfer and secondary ion formation through non-thermodynamic surface ionization. 86 refs., 20 figs

On-chip electromembrane extraction for monitoring drug metabolism in real time by electrospray ionization mass spectrometry

DEFF Research Database (Denmark)

Petersen, Nickolaj J.; Pedersen, Jacob Sønderby; Poulsen, Nicklas Nørgård

2012-01-01

A temperature controlled (37 °C) metabolic reaction chamber with a volume of 1 mL was coupled directly to electrospray ionization mass spectrometry (ESI-MS) by the use of a 50 µm deep counter flow micro-chip electromembrane extraction (EME) system. The EME/ESI-MS system was used to study the in v......A temperature controlled (37 °C) metabolic reaction chamber with a volume of 1 mL was coupled directly to electrospray ionization mass spectrometry (ESI-MS) by the use of a 50 µm deep counter flow micro-chip electromembrane extraction (EME) system. The EME/ESI-MS system was used to study...

Mass spectral analysis of N-oxides of Chemical Weapons Convention related aminoethanols under electrospray ionization conditions.

Science.gov (United States)

Sridhar, L; Karthikraj, R; Murty, M R V S; Raju, N Prasada; Vairamani, M; Prabhakar, S

2011-02-28

N,N'-Dialkylaminoethanols are the hydrolyzed products or precursors of chemical warfare agents such as V-agents and nitrogen mustards, and they are prone to undergo oxidation in environmental matrices or during decontamination processes. Consequently, screening of the oxidized products of aminoethanols in aqueous samples is an important task in the verification of chemical weapons convention-related chemicals. Here we report the successful characterization of the N-oxides of N,N'-dialkylaminoethanols, alkyl diethanolamines, and triethanolamine using positive ion electrospray ionization mass spectrometry. The collision-induced dissociation (CID) spectra of the [M+H](+) and [M+Na](+) ions show diagnostic product ions that enable the unambiguous identification of the studied N-oxides, including those of isomeric compounds. The proposed fragmentation pathways are supported by high-resolution mass spectrometry data and product/precursor ion spectra. The CID spectra of [M+H](+) ions included [MH-CH(4)O(2)](+) as the key product ion, in addition to a distinctive alkene loss that allowed us to recognize the alkyl group attached to the nitrogen. The [M+Na](+) ions show characteristic product ions due to the loss of groups (R) attached to nitrogen either as a radical (R) or as a molecule [R+H or (R-H)] after hydrogen migration. Copyright © 2011 John Wiley & Sons, Ltd.

Liquid Chromatography with Post-Column Reagent Addition of Ammonia in Methanol Coupled to Negative Ion Electrospray Ionization Tandem Mass Spectrometry for Determination of Phenoxyacid Herbicides and their Degradation Products in Surface Water

Directory of Open Access Journals (Sweden)

Renata Raina

2010-01-01

Full Text Available A new liquid chromatography (LC-negative ion electrospray ionization (ESI − –tandem mass spectrometry (MS/MS method with post-column addition of ammonia in methanol has been developed for the analysis of acid herbicides: 2,4-dichlorophenoxy acetic acid, 4-chloro-o-tolyloxyacetic acid, 2-(2-methyl-4-chlorophenoxybutyric acid, mecoprop, dichlorprop, 4-(2,4-dichlorophenoxy butyric acid, 2,4,5-trichlorophenoxy propionic acid, dicamba and bromoxynil, along with their degradation products: 4-chloro-2-methylphenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and 3,5-dibromo-4-hydroxybenzoic acid. The samples were extracted from the surface water matrix using solid-phase extraction (SPE with a polymeric sorbent and analyzed with LC ESI − with selected reaction monitoring (SRM using a three-point confirmation approach. Chromatography was performed on a Zorbax Eclipse XDB-C18 (50 × 4.6 mm i.d., 1.8 μm with a gradient elution using water-methanol with 2 mM ammonium acetate mobile phase at a flow rate of 0.15 mL/min. Ammonia in methanol (0.8 M was added post-column at a flow rate of 0.05 mL/min to enhance ionization of the degradation products in the MS source. One SRM transition was used for quantitative analysis while the second SRM along with the ratio of SRM1/SRM2 within the relative standard deviation determined by standards for each individual pesticide and retention time match were used for confirmation. The standard deviation of ratio of SRM1/SRM2 obtained from standards run on the day of analysis for different phenoxyacid herbicides ranged from 3.9 to 18.5%. Limits of detection (LOD were between 1 and 15 ng L −1 and method detection limits (MDL with strict criteria requiring <25% deviation of peak area from best-fit line for both SRM1 and SRM2 ranged from 5 to 10 ng L −1 for acid ingredients (except dicamba at 30 ng L −1 and from 2 to 30 ng L −1 for degradation products. The SPE-LC-ESI − MS/MS method permitted low nanogram

Assessing the Interplay between the Physicochemical Parameters of Ion-Pairing Reagents and the Analyte Sequence on the Electrospray Desorption Process for Oligonucleotides

Science.gov (United States)

Basiri, Babak; Murph, Mandi M.; Bartlett, Michael G.

2017-08-01

Alkylamines are widely used as ion-pairing agents during LC-MS of oligonucleotides. In addition to a better chromatographic separation, they also assist with the desorption of oligonucleotide ions into the gas phase, cause charge state reduction, and decrease cation adduction. However, the choice of such ion-pairing agents has considerable influence on the MS signal intensity of oligonucleotides as they can also cause significant ion suppression. Interestingly, optimal ion-pairing agents should be selected on a case by case basis as their choice is strongly influenced by the sequence of the oligonucleotide under investigation. Despite imposing major practical difficulties to analytical method development, such a highly variable system that responds very strongly to the nuances of the electrospray composition provides an excellent opportunity for a fundamental study of the electrospray ionization process. Our investigations using this system quantitatively revealed the major factors that influenced the ESI ionization efficiency of oligonucleotides. Parameters such as boiling point, proton affinity, partition coefficient, water solubility, and Henry's law constants for the ion-pairing reagents and the hydrophobic thymine content of the oligonucleotides were found to be the most significant contributors. Identification of these parameters also allowed for the development of a statistical predictive algorithm that can assist with the choice of an optimum IP agent for each particular oligonucleotide sequence. We believe that research in the field of oligonucleotide bioanalysis will significantly benefit from this algorithm (included in Supplementary Material) as it advocates for the use of lesser-known but more suitable ion-pair alternatives to TEA for many oligonucleotide sequences.

Desorption electrospray ionization mass spectrometry for trace analysis of agrochemicals in food.

Science.gov (United States)

García-Reyes, Juan F; Jackson, Ayanna U; Molina-Díaz, Antonio; Cooks, R Graham

2009-01-15

Desorption electrospray ionization (DESI) is applied to the rapid, in situ, direct qualitative and quantitative (ultra)trace analysis of agrochemicals in foodstuffs. To evaluate the potential of DESI mass spectrometry (MS) in toxic residue testing in food, 16 representative multiclass agricultural chemicals (pesticides, insecticides, herbicides, and fungicides) were selected (namely, ametryn, amitraz, azoxystrobin, bitertanol, buprofezin, imazalil, imazalil metabolite, isofenphos-methyl, malathion, nitenpyram, prochloraz, spinosad, terbuthylazine, thiabendazole, and thiacloprid). The DESI-MS experiments were performed using 3 microL of solution spotted onto conventional smooth poly(tetrafluoroethylene) (PTFE) surfaces, with examination by MS and tandem mass spectrometry (MS/MS) using an ion trap mass spectrometer. Optimization of the spray solvent led to the use of acetonitrile/water (80:20) (v/v), with 1% formic acid. Most of the compounds tested showed remarkable sensitivity in the positive ion mode, approaching that attainable with conventional direct infusion electrospray mass spectrometry. To evaluate the potential of the proposed approach in real samples, different experiments were performed including the direct DESI-MS/MS analysis of fruit peels and also of fruit/vegetable extracts. The results proved that DESI allows the detection and confirmation of traces of agrochemicals in actual market-purchased samples. In addition, MS/MS confirmation of selected pesticides in spiked vegetable extracts was obtained at absolute levels as low as 1 pg for ametryn. Quantitation of imazalil residues was also undertaken using an isotopically labeled standard. The data obtained were in agreement with those from the liquid chromatography mass spectrometry (LC-MS) reference method, with relative standard deviation (RSD) values consistently below 15%. The results obtained demonstrate the sensitivity of DESI as they meet the stringent European Union pesticide regulation

Complexation of malic acid with cadmium(II) probed by electrospray ionization mass spectrometry

Czech Academy of Sciences Publication Activity Database

Jaklová Dytrtová, Jana; Jakl, M.; Schröder, Detlef

2012-01-01

Roč. 90, 15 Feb (2012), s. 63-68 ISSN 0039-9140 Institutional research plan: CEZ:AV0Z40550506 Keywords : electrospray ionization * hazardous metal s * mass spectrometry * root exudates * soil solution Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.498, year: 2012

Application of silicon nanowires and indium tin oxide surfaces in desorption electrospray ionization

Czech Academy of Sciences Publication Activity Database

Pól, Jaroslav; Novák, Petr; Volný, Michael; Kruppa, G. H.; Kostiainen, R.; Lemr, Karel; Havlíček, Vladimír

2008-01-01

Roč. 14, č. 6 (2008), s. 391-399 ISSN 1469-0667 R&D Projects: GA MŠk LC07017 Institutional research plan: CEZ:AV0Z50200510 Keywords : mass spectrometry * desorption electrospray ionization * nanowires Subject RIV: CE - Biochemistry Impact factor: 1.167, year: 2008

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

NARCIS (Netherlands)

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

2004-01-01

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

Online quench-flow electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry for elucidating kinetic and chemical enzymatic reaction mechanisms.

Science.gov (United States)

Clarke, David J; Stokes, Adam A; Langridge-Smith, Pat; Mackay, C Logan

2010-03-01

We have developed an automated quench-flow microreactor which interfaces directly to an electrospray ionization (ESI) mass spectrometer. We have used this device in conjunction with ESI Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) to demonstrate the potential of this approach for studying the mechanistic details of enzyme reactions. For the model system chosen to test this device, namely, the pre-steady-state hydrolysis of p-nitrophenyl acetate by the enzyme chymotrypsin, the kinetic parameters obtained are in good agreement with those in the literature. To our knowledge, this is the first reported use of online quench-flow coupled with FTICR MS. Furthermore, we have exploited the power of FTICR MS to interrogate the quenched covalently bound enzyme intermediate using top-down fragmentation. The accurate mass capabilities of FTICR MS permitted the nature of the intermediate to be assigned with high confidence. Electron capture dissociation (ECD) fragmentation allowed us to locate the intermediate to a five amino acid section of the protein--which includes the known catalytic residue, Ser(195). This experimental approach, which uniquely can provide both kinetic and chemical details of enzyme mechanisms, is a potentially powerful tool for studies of enzyme catalysis.

A new concept positive (negative) surface ionization source for RIB applications

International Nuclear Information System (INIS)

Alton, G.D.; Welton, R.F.; Cui, B.

1996-01-01

A versatile, new concept, spherical-geometry, positive (negative) surface-ionization source has been designed. fabricated, and tests completed which can operate in either positive- or negative-ion beam generation modes without mechanical changes to the source. The highly permeable, composite Ir/C has an intrinsic work function of 0 = 5.29 eV and can be used directly for the generation of positive-ion beams of highly electropositive elements. For negative-surface ionization, the work function is lowered by dynamic flow of a highly electropositive adsorbate such as Cs through the ionizer matrix. The results of initial testing indicate that the source is reliable, stable and easy to operate, with efficiencies for Cs + estimated to exceed 60% and as high as ∼50% for F - generation. The design features, operational principles, and initial performance of the source for generating Cs + and F - , when operated with Cs, are discussed in this article

Detection of protonated non-Watson-Crick base pairs using electrospray ionization mass spectrometry.

Science.gov (United States)

Ishida, Riyoko; Iwahashi, Hideo

2018-03-01

Many studies have shown that protonated nucleic acid base pairs are involved in a wide variety of nucleic acid structures. However, little information is available on relative stability of hemiprotonated self- and non-self-dimers at monomer level. We used electrospray ionization mass spectrometry (ESI-MS) to evaluate the relative stability under various concentrations of hydrogen ion. These enable conjecture of the formation of protonated non-Watson-Crick base pairs based on DNA and RNA base sequence. In the present study, we observed that ESI-MS peaks corresponded to respective self-dimers for all examined nucleosides except for adenosine. Peak heights depended on the concentration of hydrogen ion. The ESI-MS peak heights of the hemiprotonated cytidine dimers and the hemiprotonated thymidine dimer sharply increased with increased concentration of hydrogen ion, suggesting direct participation of hydrogen ion in dimer formations. In ESI-MS measurements of the solutions containing adenosine, cytidine, thymidine and guanosine, we observed protonated cytidine-guanosine dimer (CH+-G) and protonated cytidine-thymidine dimer (CH+-T) in addition to hemiprotonated cytidine-cytidine dimer (CH+-C) with following relative peak height, (CH+-C) > (CH+-G) ≈ (CH+-T) > (CH+-A). Additionally, in the ESI-MS measurements of solutions containing adenosine, thymidine and guanosine, we observed a considerable amount of protonated adenosine-guanosine (AH+-G) and protonated adenosine-thymidine (AH+-T).

Identification and Quantification of Flavonoids and Phenolic Acids in Burr Parsley (Caucalis platycarpos L., Using High-Performance Liquid Chromatography with Diode Array Detection and Electrospray Ionization Mass Spectrometry

Directory of Open Access Journals (Sweden)

Ana Mornar

2009-07-01

Full Text Available A sensitive method coupling high-performance liquid chromatography (HPLC with diode-array detector (DAD and electrospray ionization mass spectrometry (MS was optimized for the separation and identification of phenolic acids, flavonoid glycosides and flavonoid aglycones in the extract of burr parsley (Caucalis platycarpos L.. Fragmentation behavior of flavonoid glycosides and phenolic acids were investigated using ion trap mass spectrometry in negative electrospray ionization. The MS, MSn and UV data together with HPLC retention time (TR of phenolic acids and flavonoids allowed structural characterization of these compounds. Caffeoylquinic acid (CQA isomers, p-coumaroyl-quinic acids (p-CoQA, feruloylquinic acids (FQA, dicaffeoylquinic acids (diCQA, luteolin-7-O-rutinoside, apigenin-7-O-rutinoside as well as isolated chrysoeriol-7-O-rutinoside have been identified as constituents of C. platycarpos for the first time. An accurate, precise and sensitive LC-DAD method for quantification of four phenolic acids (3-O-caffeoylquinic, caffeic, p-coumaric, o-coumaric acid, four flavonoid glycosides (luteolin-7-O-glucoside, apigenin-7-O-glucoside, quercetin-3-O-galactoside, quercetin-3-O-rhamnoside, and three flavonoid aglycones (luteolin, apigenin, chrysoeriol in C. platycarpos extract was validated in terms of linearity, limit of detection, limit of quantification, precision and accuracy. 3-O-caffeoylquinic acid was the predominant phenolic acid and luteolin-7-O-glucoside was the predominant flavonoid glycoside.

Real-time hydrogen/deuterium exchange kinetics via supercharged electrospray ionization tandem mass spectrometry.

Science.gov (United States)

Sterling, Harry J; Williams, Evan R

2010-11-01

Amide hydrogen/deuterium exchange (HDX) rate constants of bovine ubiquitin in an ammonium acetate solution containing 1% of the electrospray ionization (ESI) "supercharging" reagent m-nitrobenzyl alcohol (m-NBA) were obtained using top-down, electron transfer dissociation (ETD) tandem mass spectrometry (MS). The supercharging reagent replaces the acid and temperature "quench" step in the conventional MS approach to HDX experiments by causing rapid protein denaturation to occur in the ESI droplet. The higher charge state ions that are produced with m-NBA are more unfolded, as measured by ion mobility, and result in higher fragmentation efficiency and higher sequence coverage with ETD. Single amino acid resolution was obtained for 44 of 72 exchangeable amide sites, and summed kinetic data were obtained for regions of the protein where adjacent fragment ions were not observed, resulting in an overall spatial resolution of 1.3 residues. Comparison of these results with previous values from NMR indicates that the supercharging reagent does not cause significant structural changes to the protein in the initial ESI solution and that scrambling or back-exchange is minimal. This new method for top-down HDX-MS enables real-time kinetic data measurements under physiological conditions, similar to those obtained using NMR, with comparable spatial resolution and significantly better sensitivity.

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

Science.gov (United States)

Stock, Naomi L.; March, Raymond E.

2014-01-01

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

Simultaneous determination of phentermine and topiramate in human plasma by liquid chromatography-tandem mass spectrometry with positive/negative ion-switching electrospray ionization and its application in pharmacokinetic study.

Science.gov (United States)

Ni, Yang; Zhou, Ying; Xu, Mingzhen; He, Xiaomeng; Li, Huqun; Haseeb, Satter; Chen, Hui; Li, Weiyong

2015-03-25

A new method for simultaneous determination of phentermine and topiramate by liquid chromatography/electrospray tandem mass spectrometry (LC/MS/MS) operated in positive and negative ionization switching modes was developed and validated. Protein precipitation with acetonitrile was selected for sample preparation. Analyses were performed on a liquid chromatography system employing a Kromasil 60-5CN column (2.1 mm × 100 mm, 5 μm) and an isocratic elution with mixed solution of acetonitrile-20mM ammonium formate containing 0.3% formic acid (40:60, v/v), at a flow rate of 0.35 mL/min. Doxazosin mesylate and pioglitazone were used as the internal standard (IS) respectively for quantification. The determination was carried out on an API 4000 triple-quadrupole mass spectrometer operated in multiple reaction monitoring (MRM) mode using the following transitions monitored simultaneously: positive m/z 150.0/91.0 for phentermine, m/z 452.1/344.3 for doxazosin, and negative m/z 338.3/77.9 for topiramate, m/z 355.0/41.9 for pioglitazone. The method was validated to be linear over the concentration range of 1-800 ng mL(-1) for phentermine, 1-1000 ng mL(-1) for topiramate. Within- and between-day accuracy and precision of the validated method at three different concentration levels were within the acceptable limits of <15% at all concentrations. Blood samples were collected into heparinized tubes before and after administration. The simple and robust LC/MS/MS method was successfully applied for the simultaneous determination of phentermine and topiramate in a pharmacokinetic study in healthy male Chinese volunteers. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecular Characterization of Thiols in Fossil Fuels by Michael Addition Reaction Derivatization and Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

Science.gov (United States)

Wang, Meng; Zhao, Suoqi; Liu, Xuxia; Shi, Quan

2016-10-04

Thiols widely occur in sediments and fossil fuels. However, the molecular composition of these compounds is unclear due to the lack of appropriate analytical methods. In this work, a characterization method for thiols in fossil fuels was developed on the basis of Michael addition reaction derivatization followed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). Model thiol compound studies showed that thiols were selectively reacted with phenylvinylsulfone and transformed to sulfones with greater than 98% conversions. This method was applied to a coker naphtha, light and heavy gas oils, and crude oils from various geological sources. The results showed that long alkyl chain thiols are readily present in petroleum, which have up to 30 carbon atoms. Large DBE dispersity of thiols indicates that naphthenic and aromatic thiols are also present in the petroleum. This method is capable of detecting thiol compounds in the part per million range by weight. This method allows characterization of thiols in a complex hydrocarbon matrix, which is complementary to the comprehensive analysis of sulfur compounds in fossil fuels.

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

Science.gov (United States)

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

2016-12-01

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.

Desorption electrospray ionization mass spectrometry in the analysis of chemical food contaminants in food

NARCIS (Netherlands)

Nielen, M.W.F.; Hooijerink, H.; Zomer, P.; Mol, J.G.J.

2011-01-01

Since its introduction, desorption electrospray ionization (DESI) mass spectrometry (MS) has been mainly applied in pharmaceutical and forensic analysis. We expect that DESI will find its way in many different fields, including food analysis. In this review, we summarize DESI developments aimed at

Charge Enhancement of Single-Stranded DNA in Negative Electrospray Ionization Using the Supercharging Reagent Meta-nitrobenzyl Alcohol

Science.gov (United States)

Brahim, Bessem; Alves, Sandra; Cole, Richard B.; Tabet, Jean-Claude

2013-12-01

Charge enhancement of single-stranded oligonucleotide ions in negative ESI mode is investigated. The employed reagent, meta-nitrobenzyl alcohol (m-NBA), was found to improve total signal intensity (Itot), increase the highest observed charge states (zhigh), and raise the average charge states (zavg) of all tested oligonucleotides analyzed in negative ESI. To quantify these increases, signal enhancement ratios (SER1%) and charge enhancement coefficients (CEC1%) were introduced. The SER1%, (defined as the quotient of total oligonucleotide ion abundances with 1 % m-NBA divided by total oligonucleotide abundance without m-NBA) was found to be greater than unity for every oligonucleotide tested. The CEC1% values (defined as the average charge state in the presence of 1 % m-NBA minus the average charge state in the absence of m-NBA) were found to be uniformly positive. Upon close inspection, the degree of charge enhancement for longer oligonucleotides was found to be dependent upon thymine density (i.e., the number and the location of phospho-thymidine units). A correlation between the charge enhancement induced by the presence of m-NBA and the apparent gas-phase acidity (largely determined by the sequence of thymine units but also by the presence of protons on other nucleobases) of multiply deprotonated oligonucleotide species, was thus established. Ammonium cations appeared to be directly involved in the m-NBA supercharging mechanism, and their role seems to be consistent with previously postulated ESI mechanisms describing desorption/ionization of single-stranded DNA into the gas phase.

Characterization of Rhodamine Self-Assembled Films Using Desorption Electrospray Ionization Mass Spectrometry

Science.gov (United States)

Shi, Ruixia; Na, Na; Jiang, Fubin; Ouyang, Jin

2013-06-01

Growth process information and molecular structure identification are very important for characterization of self-assembled films. Here, we explore the possible application of desorption electrospray ionization mass spectrometry (DESI-MS) that provides the assembled information of rhodamine B (Rh B) and rhodamine 123 (Rh 123) films. With the help of lab-made DESI source, two characteristic ions [Rh B]+ and [Rh 123]+ are observed directly in the open environment. To evaluate the reliability of this technique, a comparative study of ultraviolet-visible (UV-vis) spectroscopy and our method is carried out, and the result shows good correlation. According to the signal intensity of characteristic ions, the layer-by-layer adsorption process of dyes can be monitored, and the thicknesses of multilayer films can also be comparatively determined. Combining the high sensitivity, selectivity, and speed of mass spectrometry, the selective adsorption of similar structure molecules under different pH is recognized easily from extracted ion chronograms. The variation trend of dyes signalling intensity with concentration of polyelectrolyte is studied as well, which reflects the effect of surface charge on dyes deposition. Additionally, the desorption area, surface morphology, and thicknesses of multilayer films are investigated using fluorescence microscope, scanning electron microscope (SEM), and atomic force microscopy (AFM), respectively. Because the desorption area was approximately as small as 2 mm2, the distribution situation of organic dyes in an arbitrary position could be gained rapidly, which means DESI-MS has advantages on in situ analysis.

Chemical profile of pineapple cv. Vitória in different maturation stages using electrospray ionization mass spectrometry.

Science.gov (United States)

Ogawa, Elizângela M; Costa, Helber B; Ventura, José A; Caetano, Luiz Cs; Pinto, Fernanda E; Oliveira, Bruno G; Barroso, Maria Eduarda S; Scherer, Rodrigo; Endringer, Denise C; Romão, Wanderson

2018-02-01

Pineapple is the fruit of Ananas comosus var. comosus plant, being cultivated in tropical areas and has high energy content and nutritional value. Herein, 30 samples of pineapple cv. Vitória were analyzed as a function of the maturation stage (0-5) and their physico-chemical parameters monitored. In addition, negative-ion mode electrospray ionization mass spectrometry [ESI(-)FT-ICR MS] was used to identify and semi-quantify primary and secondary metabolites present in the crude and phenolic extracts of pineapple, respectively. Physico-chemical tests show an increase in the total soluble solids (TSS) values and in the TSS/total titratable acidity ratio as a function of the maturity stage, where a maximum value was observed in stage 3 (¾ of the fruit is yellow, which corresponds to the color of the fruit peel). ESI(-)FT-ICR MS analysis for crude extracts showed the presence mainly of sugars as primary metabolites present in deprotonated molecule form ([M - H] - and [2 M - H] - ions) whereas, for phenolic fractions, 11 compounds were detected, being the most abundant in the third stage of maturation. This behavior was confirmed by quantitative analysis of total polyphenols. ESI-FT-ICR MS was efficient in identifying primary (carbohydrates and organic acids) and secondary metabolites (13 phenolic compounds) presents in the crude and phenolic extract of the samples, respectively. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Stabilization of Proteins and Noncovalent Protein Complexes during Electrospray Ionization by Amino Acid Additives.

Science.gov (United States)

Zhang, Hua; Lu, Haiyan; Chingin, Konstantin; Chen, Huanwen

2015-07-21

Ionization of proteins and noncovalent protein complexes with minimal disturbance to their native structure presents a great challenge for biological mass spectrometry (MS). In living organisms, the native structure of intracellular proteins is commonly stabilized by solute amino acids (AAs) accumulated in cells at very high concentrations. Inspired by nature, we hypothesized that AAs could also pose a stabilizing effect on the native structure of proteins and noncovalent protein complexes during ionization. To test this hypothesis, here we explored MS response for various protein complexes upon the addition of free AAs at mM concentrations into the electrospray ionization (ESI) solution. Thermal activation of ESI droplets in the MS inlet capillary was employed as a model destabilizing factor during ionization. Our results indicate that certain AAs, in particular proline (Pro), pose considerable positive effect on the stability of noncovalent protein complexes in ESI-MS without affecting the signal intensity of protein ions and original protein-ligand equilibrium, even when added at the 20 mM concentration. The data suggest that the degree of protein stabilization is primarily determined by the osmolytic and ampholytic characteristics of AA solutes. The highest stability and visibility of noncovalent protein complexes in ESI-MS are achieved using AA additives with neutral isoelectric point, moderate proton affinity, and unfavorable interaction with the native protein state. Overall, our results indicate that the simple addition of free amino acids into the working solution can notably improve the stability and accuracy of protein analysis by native ESI-MS.

Negative Ion Sources: Magnetron and Penning

CERN Document Server

Faircloth, D.C.

2013-12-16

The history of the magnetron and Penning electrode geometry is briefly outlined. Plasma generation by electrical discharge-driven electron impact ionization is described and the basic physics of plasma and electrodes relevant to magnetron and Penning discharges are explained. Negative ions and their applications are introduced, along with their production mechanisms. Caesium and surface production of negative ions are detailed. Technical details of how to build magnetron and Penning surface plasma sources are given, along with examples of specific sources from around the world. Failure modes are listed and lifetimes compared.

Negative Ion Sources: Magnetron and Penning

International Nuclear Information System (INIS)

Faircloth, D C

2013-01-01

The history of the magnetron and Penning electrode geometry is briefly outlined. Plasma generation by electrical discharge-driven electron impact ionization is described and the basic physics of plasma and electrodes relevant to magnetron and Penning discharges are explained. Negative ions and their applications are introduced, along with their production mechanisms. Caesium and surface production of negative ions are detailed. Technical details of how to build magnetron and Penning surface plasma sources are given, along with examples of specific sources from around the world. Failure modes are listed and lifetimes compared. (author)

The updated bottom up solution applied to atmospheric pressure photoionization and electrospray ionization mass spectrometry

Science.gov (United States)

The Updated Bottom Up Solution (UBUS) was recently applied to atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) of triacylglycerols (TAGs). This report demonstrates that the UBUS applies equally well to atmospheric pressure photoionization (APPI) MS and to electrospray ionizatio...

Delivering Transmembrane Peptide Complexes to the Gas Phase Using Nanodiscs and Electrospray Ionization

Science.gov (United States)

Li, Jun; Richards, Michele R.; Kitova, Elena N.; Klassen, John S.

2017-10-01

The gas-phase conformations of dimers of the channel-forming membrane peptide gramicidin A (GA), produced from isobutanol or aqueous solutions of GA-containing nanodiscs (NDs), are investigated using electrospray ionization-ion mobility separation-mass spectrometry (ESI-IMS-MS) and molecular dynamics (MD) simulations. The IMS arrival times measured for (2GA + 2Na)2+ ions from isobutanol reveal three different conformations, with collision cross-sections (Ω) of 683 Å2 (conformation 1, C1), 708 Å2 (C2), and 737 Å2 (C3). The addition of NH4CH3CO2 produced (2GA + 2Na)2+ and (2GA + H + Na)2+ ions, with Ω similar to those of C1, C2, and C3, as well as (2GA + 2H)2+, (2GA + 2NH4)2+, and (2GA + H + NH4)2+ ions, which adopt a single conformation with a Ω similar to that of C2. These results suggest that the nature of the charging agents, imparted by the ESI process, can influence dimer conformation in the gas phase. Notably, the POPC NDs produced exclusively (2GA + 2NH4)2+ dimer ions; the DMPC NDs produced both (2GA + 2H)2+ and (2GA + 2NH4)2+ dimer ions. While the Ω of (2GA + 2H)2+ is similar to that of C2, the (2GA + 2NH4)2+ ions from NDs adopt a more compact structure, with a Ω of 656 Å2. It is proposed that this compact structure corresponds to the ion conducting single stranded head-to-head helical GA dimer. These findings highlight the potential of NDs, combined with ESI, for transferring transmembrane peptide complexes directly from lipid bilayers to the gas phase. [Figure not available: see fulltext.

Transmission geometry laserspray ionization vacuum using an atmospheric pressure inlet.

Science.gov (United States)

Lutomski, Corinne A; El-Baba, Tarick J; Inutan, Ellen D; Manly, Cory D; Wager-Miller, James; Mackie, Ken; Trimpin, Sarah

2014-07-01

This represents the first report of laserspray ionization vacuum (LSIV) with operation directly from atmospheric pressure for use in mass spectrometry. Two different types of electrospray ionization source inlets were converted to LSIV sources by equipping the entrance of the atmospheric pressure inlet aperture with a customized cone that is sealed with a removable glass plate holding the matrix/analyte sample. A laser aligned in transmission geometry (at 180° relative to the inlet) ablates the matrix/analyte sample deposited on the vacuum side of the glass slide. Laser ablation from vacuum requires lower inlet temperature relative to laser ablation at atmospheric pressure. However, higher inlet temperature is required for high-mass analytes, for example, α-chymotrypsinogen (25.6 kDa). Labile compounds such as gangliosides and cardiolipins are detected in the negative ion mode directly from mouse brain tissue as intact doubly deprotonated ions. Multiple charging enhances the ion mobility spectrometry separation of ions derived from complex tissue samples.

Ionization in matrix-assisted laser desorption/ionization: singly charged molecular ions are the lucky survivors.

Science.gov (United States)

Karas, M; Glückmann, M; Schäfer, J

2000-01-01

A new model for the ionization processes in UV matrix-assisted laser desorption/ionization (MALDI) which accounts for the major phenomena observed is presented and discussed. The model retains elements of earlier approaches, such as photoionization and photochemical reactions, but it redefines these in the light of new working questions, most importantly why only singly charged ions are detected. Based on experimental evidence, the formation of singly and multiply charged clusters by a deficiency/excess of ions and also by photoionization and subsequent photochemical processes is pointed out to be the major ionization processes, which typically occur in parallel. The generation of electrons and their partial loss into the surrounding vacuum and solid, on the one hand, results in a positively charged ion-neutral plume facilitating a high overall ionization yield. On the other hand, these electrons, and also the large excess of protonated matrix ions in the negative ion mode, induce effective ion reneutralization in the plume. These neutralization processes are most effective for the highly charged cluster ions initially formed. Their fragmentation behaviour is evidenced in fast metastable fragmentation characteristics and agrees well with an electron capture dissociation mechanism and the enthalpy transfer upon neutralization forms the rationale for the prominent fragmentation and intense chemical noise accompanying successful MALDI. Within the course of the paper, cross-correlations with other desorption/ionization techniques and with earlier discussions on their mechanisms are drawn. Copyright 2000 John Wiley & Sons, Ltd.

Probe-Substrate Distance Control in Desorption Electrospray Ionization

Science.gov (United States)

Yarger, Tyler J.; Yuill, Elizabeth M.; Baker, Lane A.

2018-03-01

We introduce probe-substrate distance (Dps)-control to desorption electrospray ionization (DESI) and report a systematic investigation of key experimental parameters. Examination of voltage, flow rate, and nebulizing gas pressure suggests as Dps decreases, the distance-dependent spray current increases, until a critical point. At the critical point the relationship inverts, and the spray current decreases as the probe moves closer to the surface due to constriction of solution flow by the nebulizing gas. Dps control was used to explore the use of spray current as a signal for feedback positioning, while mass spectrometry imaging was performed simultaneously. Further development of this technique is expected to find application in study of structure-function relationships for clinical diagnostics, biological investigation, and materials characterization. [Figure not available: see fulltext.

Ejection of solvated ions from electrosprayed methanol/water nanodroplets studied by molecular dynamics simulations.

Science.gov (United States)

Ahadi, Elias; Konermann, Lars

2011-06-22

The ejection of solvated small ions from nanometer-sized droplets plays a central role during electrospray ionization (ESI). Molecular dynamics (MD) simulations can provide insights into the nanodroplet behavior. Earlier MD studies have largely focused on aqueous systems, whereas most practical ESI applications involve the use of organic cosolvents. We conduct simulations on mixed water/methanol droplets that carry excess NH(4)(+) ions. Methanol is found to compromise the H-bonding network, resulting in greatly increased rates of ion ejection and solvent evaporation. Considerable differences in the water and methanol escape rates cause time-dependent changes in droplet composition. Segregation occurs at low methanol concentration, such that layered droplets with a methanol-enriched periphery are formed. This phenomenon will enhance the partitioning of analyte molecules, with possible implications for their ESI efficiencies. Solvated ions are ejected from the tip of surface protrusions. Solvent bridging prior to ion secession is more extensive for methanol/water droplets than for purely aqueous systems. The ejection of solvated NH(4)(+) is visualized as diffusion-mediated escape from a metastable basin. The process involves thermally activated crossing of a ~30 kJ mol(-1) free energy barrier, in close agreement with the predictions of the classical ion evaporation model.

Use of an Open Port Sampling Interface Coupled to Electrospray Ionization for the On-Line Analysis of Organic Aerosol Particles

Science.gov (United States)

Swanson, Kenneth D.; Worth, Anne L.; Glish, Gary L.

2018-02-01

A simple design for an open port sampling interface coupled to electrospray ionization (OPSI-ESI) is presented for the analysis of organic aerosols. The design uses minimal modifications to a Bruker electrospray (ESI) emitter to create a continuous flow, self-aspirating open port sampling interface. Considerations are presented for introducing aerosol to the open port sampling interface including aerosol gas flow and solvent flow rates. The device has been demonstrated for use with an aerosol of nicotine as well as aerosol formed in the pyrolysis of biomass. Upon comparison with extractive electrospray ionization (EESI), this device has similar sensitivity with increased reproducibility by nearly a factor of three. The device has the form factor of a standard Bruker/Agilent ESI emitter and can be used without any further instrument modifications.

Examination and Manipulation of Protein Surface Charge in Solution with Electrospray Ionization Mass Spectrometry

Science.gov (United States)

Gross, Deborah S.; Van Ryswyk, Hal

2014-01-01

Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool for examining the charge of proteins in solution. The charge can be manipulated through choice of solvent and pH. Furthermore, solution-accessible, protonated lysine side chains can be specifically tagged with 18-crown-6 ether to form noncovalent adducts. Chemical derivatization…

Molecular identification of Mucorales in human tissues: contribution of PCR electrospray-ionization mass spectrometry.

Science.gov (United States)

Alanio, A; Garcia-Hermoso, D; Mercier-Delarue, S; Lanternier, F; Gits-Muselli, M; Menotti, J; Denis, B; Bergeron, A; Legrand, M; Lortholary, O; Bretagne, S

2015-06-01

Molecular methods are crucial for mucormycosis diagnosis because cultures are frequently negative, even if microscopy suggests the presence of hyphae in tissues. We assessed PCR/electrospray-ionization mass spectrometry (PCR/ESI-MS) for Mucorales identification in 19 unfixed tissue samples from 13 patients with proven or probable mucormycosis and compared the results with culture, quantitative real-time PCR, 16S-23S rRNA gene internal transcribed spacer region (ITS PCR) and 18S PCR sequencing. Concordance with culture identification to both genus and species levels was higher for PCR/ESI-MS than for the other techniques. Thus, PCR/ESI-MS is suitable for Mucorales identification, within 6 hours, for tissue samples for which microscopy results suggest the presence of hyphae. Copyright © 2015 European Society of Clinical Microbiology and Infectious Diseases. Published by Elsevier Ltd. All rights reserved.

Electrospray ionization mass spectrometry and partial least squares discriminant analysis applied to the quality control of olive oil.

Science.gov (United States)

Alves, Junia O; Botelho, Bruno G; Sena, Marcelo M; Augusti, Rodinei

2013-10-01

Direct infusion electrospray ionization mass spectrometry in the positive ion mode [ESI(+)-MS] is used to obtain fingerprints of aqueous-methanolic extracts of two types of olive oils, extra virgin (EV) and ordinary (OR), as well as of samples of EV olive oil adulterated by the addition of OR olive oil and other edible oils: corn (CO), sunflower (SF), soybean (SO) and canola (CA). The MS data is treated by the partial least squares discriminant analysis (PLS-DA) protocol aiming at discriminating the above-mentioned classes formed by the genuine olive oils, EV (1) and OR (2), as well as the EV adulterated samples, i.e. EV/SO (3), EV/CO (4), EV/SF (5), EV/CA (6) and EV/OR (7). The PLS-DA model employed is built with 190 and 70 samples for the training and test sets, respectively. For all classes (1-7), EV and OR olive oils as well as the adulterated samples (in a proportion varying from 0.5 to 20.0% w/w) are properly classified. The developed methodology required no ions identification and demonstrated to be fast, as each measurement lasted about 3 min including the extraction step and MS analysis, and reliable, because high sensitivities (rate of true positives) and specificities (rate of true negatives) were achieved. Finally, it can be envisaged that this approach has potential to be applied in quality control of EV olive oils. Copyright © 2013 John Wiley & Sons, Ltd.

Negative Ion In-Source Decay Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry for Sequencing Acidic Peptides

Science.gov (United States)

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.

Surface generation of negative hydrogen ion beams

International Nuclear Information System (INIS)

Bommel, P.J.M. van.

1984-01-01

This thesis describes investigations on negative hydrogen ion sources at the ampere level. Formation of H - ions occurs when positive hydrogen ions capture two electrons at metal surfaces. The negative ionization probability of hydrogen at metal surfaces increases strongly with decreasing work function of the surface. The converters used in this study are covered with cesium. Usually there are 'surface plasma sources' in which the hydrogen source plasma interacts with a converter. In this thesis the author concentrates upon investigating a new concept that has converters outside the plasma. In this approach a positive hydrogen ion beam is extracted from the plasma and is subsequently reflected from a low work function converter surface. (Auth.)

Identifying the related compounds using electrospray ionization tandem mass spectrometry: bromotyrosine alkaloids from marine sponge Psammaplysilla purpurea

Digital Repository Service at National Institute of Oceanography (India)

Tilvi, S.; DeSouza, L.

electrospray ionization tandem mass spectrometry (ESI-MS/MS). This sponge has tremendous chemical diversity of bromotyrosine alkaloids. Here we have used the proteomics approach in identifying related bromotyrosine alkaloids based on the predicated mass...

Electrospray ionization deposition of BSA under vacuum conditions

Science.gov (United States)

Hecker, Dominic; Gloess, Daniel; Frach, Peter; Gerlach, Gerald

2015-05-01

Vacuum deposition techniques like thermal evaporation and CVD with their precise layer control and high layer purity often cannot be applied for the deposition of chemical or biological molecules. The molecules are usually decomposed by heat. To overcome this problem, the Electrospray ionization (ESI) process known from mass spectroscopy is employed to transfer molecules into vacuum and to deposit them on a substrate. In this work, a homemade ESI tool was used to deposit BSA (Bovine serum albumin) layers with high deposition rates. Solutions with different concentrations of BSA were prepared using a methanol:water (MeOH:H2O) mixture (1:1) as solvent. The influence of the substrate distance on the deposition rate and on the transmission current was analyzed. Furthermore, the layer thickness distribution and layer adhesion were investigated.

A Comparison of Alternating Current and Direct Current Electrospray Ionization for Mass Spectrometry

Science.gov (United States)

Sarver, Scott A.; Chetwani, Nishant; Dovichi, Norman J.; Go, David B.; Gartner, Carlos A.

2014-04-01

A series of studies comparing the performance of alternating current electrospray ionization (AC ESI) mass spectrometry (MS) and direct current electrospray ionization (DC ESI) MS have been conducted, exploring the absolute signal intensity and signal-to-background ratios produced by both methods using caffeine and a model peptide as targets. Because the high-voltage AC signal was more susceptible to generating gas discharges, the operating voltage range of AC ESI was significantly smaller than that for DC ESI, such that the absolute signal intensities produced by DC ESI at peak voltages were one to two orders of magnitude greater than those for AC ESI. Using an electronegative nebulizing gas, sulfur hexafluoride (SF6), instead of nitrogen (N2) increased the operating range of AC ESI by ~50 %, but did not appreciably improve signal intensities. While DC ESI generated far greater signal intensities, both ionization methods produced comparable signal-to-background noise, with AC ESI spectra appearing qualitatively cleaner. A quantitative calibration analysis was performed for two analytes, caffeine and the peptide MRFA. AC ESI utilizing SF6 outperforms all other techniques for the detection of MRFA, producing chromatographic limits of detection nearly one order of magnitude lower than that of DC ESI utilizing N2, and one-half that of DC ESI utilizing SF6. However, DC ESI outperforms AC ESI for the analysis of caffeine, indicating that improvements in spectral quality may benefit certain compounds or classes of compounds, on an individual basis.

Resonance Ionization Laser Ion Sources

CERN Document Server

Marsh, B

2013-01-01

The application of the technique of laser resonance ionization to the production of singly charged ions at radioactive ion beam facilities is discussed. The ability to combine high efficiency and element selectivity makes a resonance ionization laser ion source (RILIS) an important component of many radioactive ion beam facilities. At CERN, for example, the RILIS is the most commonly used ion source of the ISOLDE facility, with a yearly operating time of up to 3000 hours. For some isotopes the RILIS can also be used as a fast and sensitive laser spectroscopy tool, provided that the spectral resolution is sufficiently high to reveal the influence of nuclear structure on the atomic spectra. This enables the study of nuclear properties of isotopes with production rates even lower than one ion per second and, in some cases, enables isomer selective ionization. The solutions available for the implementation of resonance laser ionization at radioactive ion beam facilities are summarized. Aspects such as the laser r...

Charge Inversion of Phospholipids by Dimetal Complexes for Positive Ion-Mode Electrospray Ionization Mass Spectrometry Analysis

DEFF Research Database (Denmark)

Svane, Simon; Gorshkov, Vladimir; Kjeldsen, Frank

2015-01-01

charges per phosphate group. Three different phosphoinositide phosphates (mono-, di-, and triphosphorylated inositides), a phosphatidic acid, a phosphatidylcholine, a phosphatidylethanolamine, and a phosphatidylglycerol were investigated. The intensities obtained in positive ion-mode of phosphoinositide...... phosphates and phosphatidic acid bound to {LGa2}(5+) were between 2.5- and 116-fold higher than that of the unmodified lipids in the negative ion-mode. Native phosphoinositide ions yielded upon CID in the negative ion-mode predominantly product ions due to losses of H3PO4, PO3(-) and H2O. In comparison, CID...

Anticodeine aptamer immobilized on a Whatman cellulose paper for thin-film microextraction of codeine from urine followed by electrospray ionization ion mobility spectrometry.

Science.gov (United States)

Hashemian, Zahra; Khayamian, Taghi; Saraji, Mohammad

2015-02-01

A combination of thin-film microextaction based on an aptamer immobilized on modified Whatman cellulose paper followed by electrospray ionization ion mobility spectrometry has been developed for the analysis of codeine in urine samples. The immobilization is based on the covalent linking of an amino-modified anticodeine aptamer to aldehyde groups of the oxidized cellulose paper. The covalent bonds were examined by infrared spectroscopy and elemental analysis. The effect of the extraction parameters, including the elution conditions (solvent type and volume), extraction time, and extraction temperature, on the extraction efficiency were investigated. Under the optimized conditions, the linear dynamic range was found to be 10-300 ng/mL with a detection limit of 3.4 ng/mL for codeine in urine. The relative standard deviation was 6.8% for three replicate measurements of codeine at 100 ng/mL in urine. Furthermore, the samples were analyzed with a standard method for the analysis of codeine using high-performance liquid chromatography with ultraviolet detection. The comparison of the results validates the accuracy of the proposed method as an alternative method for the analysis of codeine in urine samples.

Production of highly ionized recoil ions in heavy ion impact

International Nuclear Information System (INIS)

Tawara, H.; Tonuma, T.; Be, S.H.; Shibata, H.; Kase, M.; Kambara, T.; Kumagai, H.; Kohno, I.

1985-01-01

The production mechanisms of highly ionized recoil ions in energetic, highly charged heavy ion impact are compared with those in photon and electron impact. In addition to the innershell ionization processes which are important in photon and electron impact, the electron transfer processes are found to play a key role in heavy ion impact. In molecular targets are also observed highly ionized monoatomic ions which are believed to be produced through production of highly ionized molecular ions followed by prompt dissociation. The observed N 6+ ions produced in 1.05MeV/amu Ar 12+ ions on N 2 molecules are produced through, for example, N 2 12+ *→N 6+ +N 6+ process. (author)

Quantification of piperazine phosphate in human plasma by high-performance liquid chromatography-electrospray ionization tandem mass spectrometry employing precolumn derivatization with dansyl chloride.

Science.gov (United States)

Lin, Hui; Tian, Yuan; Zhang, Zunjian; Wu, Lili; Chen, Yun

2010-04-01

This paper describes a novel method that combines dansyl chloride (DNS-CL) derivatization with high-performance liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI/MS/MS) for the sensitive and selective determination of piperazine phosphate in human plasma. After addition of ondansetron hydrochloride as internal standard (IS), piperazine phosphate was derivatized and then extracted with ethyl acetate. After being evaporated and reconstituted, the sample was analyzed using LC-ESI/MS/MS. Separation was achieved using an Agilent ZORBAX SB-C(18) (150 mm x 2.1 mm I.D., 3.5 microm) column and isocratic elution with 10 mM ammonium acetate solution (pH 3.0)-methanol (50: 50, v/v). Detection was performed on a triple-quadrupole mass spectrometer utilizing electrospray ionization (ESI) interface operating in positive ion and selected reaction monitoring (SRM) mode with the precursor to product ion transitions m/z 320-->171 for DNS-CL-piperazine phosphate and m/z 294-->170 for the IS. The method was fully validated for its selectivity, sensitivity, linearity, precision, accuracy, recovery, matrix effect and stability. The coefficient (r) of piperazine phosphate with a linear range of 0.1-15 microg mL(-1) was 0.9974-0.9995. The limit of detection and lower limit of quantification in human plasma were 0.01 and 0.1 microg mL(-1), respectively. The validated LC-ESI/MS/MS method has been successfully applied to a bioequivalence study of piperazine phosphate trochiscus in Chinese healthy male volunteers. 2010 Elsevier B.V. All rights reserved.

Protocol for an electrospray ionization tandem mass spectral product ion library: development and application for identification of 240 pesticides in foods.

Science.gov (United States)

Zhang, Kai; Wong, Jon W; Yang, Paul; Hayward, Douglas G; Sakuma, Takeo; Zou, Yunyun; Schreiber, André; Borton, Christopher; Nguyen, Tung-Vi; Kaushik, Banerjee; Oulkar, Dasharath

2012-07-03

Modern determination techniques for pesticides must yield identification quickly with high confidence for timely enforcement of tolerances. A protocol for the collection of liquid chromatography (LC) electrospray ionization (ESI)-quadruple linear ion trap (Q-LIT) mass spectrometry (MS) library spectra was developed. Following the protocol, an enhanced product ion (EPI) library of 240 pesticides was developed by use of spectra collected from two laboratories. A LC-Q-LIT-MS workflow using scheduled multiple reaction monitoring (sMRM) survey scan, information-dependent acquisition (IDA) triggered collection of EPI spectra, and library search was developed and tested to identify the 240 target pesticides in one single LC-Q-LIT MS analysis. By use of LC retention time, one sMRM survey scan transition, and a library search, 75-87% of the 240 pesticides were identified in a single LC/MS analysis at fortified concentrations of 10 ng/g in 18 different foods. A conventional approach with LC-MS/MS using two MRM transitions produced the same identifications and comparable quantitative results with the same incurred foods as the LC-Q-LIT using EPI library search, finding 1.2-49 ng/g of either carbaryl, carbendazim, fenbuconazole, propiconazole, or pyridaben in peaches; carbendazim, imazalil, terbutryn, and thiabendazole in oranges; terbutryn in salmon; and azoxystrobin in ginseng. Incurred broccoli, cabbage, and kale were screened with the same EPI library using three LC-Q-LIT and a LC-quadruple time-of-flight (Q-TOF) instruments. The library search identified azoxystrobin, cyprodinil, fludioxinil, imidacloprid, metalaxyl, spinosyn A, D, and J, amd spirotetramat with each instrument. The approach has a broad application in LC-MS/MS type targeted screening in food analysis.

Power of Ultra Performance Liquid Chromatography/Electrospray Ionization-MS Reconstructed Ion Chromatograms in the Characterization of Small Differences in Polymer Microstructure.

Science.gov (United States)

Epping, Ruben; Panne, Ulrich; Falkenhagen, Jana

2018-03-06

From simple homopolymers to functionalized, 3-dimensional structured copolymers, the complexity of polymeric materials has become more and more sophisticated. With new applications, for instance, in the semiconductor or pharmaceutical industry, the requirements for the characterization have risen with the complexity of the used polymers. For each additional distribution, an additional dimension in analysis is needed. Small, often isomeric heterogeneities in topology or microstructure can usually not be simply separated chromatographically or distinguished by any common detector but affect the properties of materials significantly. For a drug delivery system, for example, the degree of branching and branching distribution is crucial for the formation of micelles. Instead of a complicated, time-consuming, and/or expensive 2D-chromatography or ion mobility spectrometry (IMS) method, that also has its limitations, in this work, a simple approach using size exclusion chromatography (SEC) coupled with electrospray ionization (ESI) mass spectrometry is proposed. The online coupling allows the analysis of reconstructed ion chromatograms (RICs) of each degree of polymerization. While a complete separation often cannot be achieved, the derived retention times and peak widths lead to information on the existence and dispersity of heterogeneities. Although some microstructural heterogeneities like short chain branching can for large polymers be characterized with methods such as light scattering, for oligomers where the heterogeneities just start to form and their influence is at the maximum, they are inaccessible with these methods. It is also shown that with a proper calibration even quantitative information can be obtained. This method is suitable to detect small differences in, e.g., branching, 3D-structure, monomer sequence, or tacticity and could potentially be used in routine analysis to quickly determine deviations.

Fine structure and ionization energy of the 1s2s2p 4P state of the helium negative ion He-.

Science.gov (United States)

Wang, Liming; Li, Chun; Yan, Zong-Chao; Drake, G W F

2014-12-31

The fine structure and ionization energy of the 1s2s2p (4)P state of the helium negative ion He(-) are calculated in Hylleraas coordinates, including relativistic and QED corrections up to O(α(4)mc(2)), O((μ/M)α(4)mc(2)), O(α(5)mc(2)), and O((μ/M)α(5)mc(2)). Higher order corrections are estimated for the ionization energy. A comparison is made with other calculations and experiments. We find that the present results for the fine structure splittings agree with experiment very well. However, the calculated ionization energy deviates from the experimental result by about 1 standard deviation. The estimated theoretical uncertainty in the ionization energy is much less than the experimental accuracy.

Confirmatory analysis method for zeranol, its metabolites and related mycotoxins in urine by liquid chromatography-negative ion electrospray tandem mass spectrometry

International Nuclear Information System (INIS)

Bennekom, E.O. van; Brouwer, L.; Laurant, E.H.M.; Hooijerink, H.; Nielen, M.W.F.

2002-01-01

The determination of the banned anabolic substance zeranol and the metabolites taleranol and zearalanone in bovine urine is complicated by the occurrence of the structurally-related mycotoxin zearalenone and the corresponding α- and β-zearalenol metabolites which possess similar estrogenic properties. A liquid chromatography-negative ion electrospray tandem mass spectrometric method is presented for the confirmatory analysis of all six resorcylic acid lactones ('zeranols') in urine samples using deuterium-labelled internal standards. The method was validated as a confirmatory method for bovine urine samples according to new draft EU guidelines and showed good precision and linearity, and CCα and CCβ values of 0.02-0.30 and -1 , respectively. The applicability was demonstrated by comparing the results of an incurred sample with previous results on the same sample obtained by gas chromatography high resolution mass spectrometry. Preliminary data show that following a simple matrix solid phase dispersion clean-up, liver samples from poultry will be amenable to this method as well

Atmospheric pressure ionization-tandem mass spectrometry of the phenicol drug family.

Science.gov (United States)

Alechaga, Élida; Moyano, Encarnación; Galceran, M Teresa

2013-11-01

In this work, the mass spectrometry behaviour of the veterinary drug family of phenicols, including chloramphenicol (CAP) and its related compounds thiamphenicol (TAP), florfenicol (FF) and FF amine (FFA), was studied. Several atmospheric pressure ionization sources, electrospray (ESI), atmospheric pressure chemical ionization and atmospheric pressure photoionization were compared. In all atmospheric pressure ionization sources, CAP, TAP and FF were ionized in both positive and negative modes; while for the metabolite FFA, only positive ionization was possible. In general, in positive mode, [M + H](+) dominated the mass spectrum for FFA, while the other compounds, CAP, TAP and FF, with lower proton affinity showed intense adducts with species present in the mobile phase. In negative mode, ESI and atmospheric pressure photoionization showed the deprotonated molecule [M-H](-), while atmospheric pressure chemical ionization provided the radical molecular ion by electron capture. All these ions were characterized by tandem mass spectrometry using the combined information obtained by multistage mass spectrometry and high-resolution mass spectrometry in a quadrupole-Orbitrap instrument. In general, the fragmentation occurred via cyclization and losses or fragmentation of the N-(alkyl)acetamide group, and common fragmentation pathways were established for this family of compounds. A new chemical structure for the product ion at m/z 257 for CAP, on the basis of the MS(3) and MS(4) spectra is proposed. Thermally assisted ESI and selected reaction monitoring are proposed for the determination of these compounds by ultra high-performance liquid chromatography coupled to tandem mass spectrometry, achieving instrumental detection limits down to 0.1 pg. Copyright © 2013 John Wiley & Sons, Ltd.

Separation and characterization of unknown impurities and isomers in flomoxef sodium by LC-IT-TOF MS and study of their negative-ion fragmentation regularities.

Science.gov (United States)

Yu, Xu; Wang, Fan; Li, Jiani; Shan, Weiguang; Zhu, Bingqi; Wang, Jian

2017-06-05

Thirteen unknown impurities in flomoxef sodium were separated and characterized by liquid chromatography coupled with high resolution ion trap/time-of-flight mass spectrometry (LC-IT-TOF MS)with positive and negative modes of electrospray ionization method for further improvement of official monographs in pharmacopoeias. The fragmentation patterns of impurities in flomoxef in the negative ion mode were studied in detail, and new negative-ion fragmentation regularities were discovered. Chromatographic separation was performed on a Kromasil C18 column (250mm×4.6mm, 5μm). The mobile phase consisted of (A) ammonium formate aqueous solution (10mM)-methanol (84:16, v/v) and (B) ammonium formate aqueous solution (10mM)-methanol (47:53, v/v). In order to determine the m/z values of the molecular ions and formulas of all detected impurities, full scan LC-MS in both positive and negative ion modes was firstly executed to obtain the m/z value of the molecules. Then LC-MS 2 and LC-MS 3 were carried out on target compounds to obtain as much structural information as possible. Complete fragmentation patterns of impurities were studied and used to obtain information about the structures of these impurities. Structures of thirteen unknown degradation products in flomoxef sodium were deduced based on the high resolution MS n data with both positive and negative modes. The forming mechanisms of degradation products in flomoxef sodium were also studied. Copyright © 2017. Published by Elsevier B.V.

On the mechanism of extractive electrospray ionization (EESI) in the dual-spray configuration.

Science.gov (United States)

Wang, Rui; Gröhn, Arto Juhani; Zhu, Liang; Dietiker, Rolf; Wegner, Karsten; Günther, Detlef; Zenobi, Renato

2012-03-01

Dual-spray extractive electrospray ionization (EESI) mass spectrometry as a versatile analytical technique has attracted much interest due to its advantages over conventional electrospray ionization (ESI). The crucial difference between EESI and ESI is that in the EESI process, the analytes are introduced in nebulized form via a neutral spray and ionized by collisions with the charged droplets from an ESI source formed by spraying pure solvent. However, the mechanism of the droplet-droplet interactions in the EESI process is still not well understood. For example, it is unclear which type of droplet-droplet interaction is dominant: bounce, coalescence, disruption, or fragmentation? In this work, droplet-droplet interaction was investigated in detail based on a theoretical model. Phase Doppler anemometry (PDA) was employed to investigate the droplet behavior in the EESI plume and provide the experimental data (droplet size and velocity) necessary for theoretical analysis. Furthermore, numerical simulations were performed to clarify the influence of the sheath gas flow on the EESI process. No coalescence between the droplets in the ESI spray and the droplets in the sample spray was observed using various geometries and sample flow rates. Theoretical analysis, together with the PDA results, suggests that droplet fragmentation may be the dominant type of droplet-droplet interaction in the EESI. The interaction time between the ESI droplet and the sample droplet was estimated to be <5 μs. This work gives a clear picture of droplet-droplet interactions in the dual-spray EESI process and detailed information for the optimization of this method for future applications that require higher sensitivity.

Characterization of a Distributed Plasma Ionization Source (DPIS) for Ion Mobility Spectrometry and Mass Spectrometry

International Nuclear Information System (INIS)

Waltman, Melanie J.; Dwivedi, Prabha; Hill, Herbert; Blanchard, William C.; Ewing, Robert G.

2008-01-01

A recently developed atmospheric pressure ionization source, a distributed plasma ionization source (DPIS), was characterized and compared to commonly used atmospheric pressure ionization sources with both mass spectrometry and ion mobility spectrometry. The source consisted of two electrodes of different sizes separated by a thin dielectric. Application of a high RF voltage across the electrodes generated plasma in air yielding both positive and negative ions depending on the polarity of the applied potential. These reactant ions subsequently ionized the analyte vapors. The reactant ions generated were similar to those created in a conventional point-to-plane corona discharge ion source. The positive reactant ions generated by the source were mass identified as being solvated protons of general formula (H2O)nH+ with (H2O)2H+ as the most abundant reactant ion. The negative reactant ions produced were mass identified primarily as CO3-, NO3-, NO2-, O3- and O2- of various relative intensities. The predominant ion and relative ion ratios varied depending upon source construction and supporting gas flow rates. A few compounds including drugs, explosives and environmental pollutants were selected to evaluate the new ionization source. The source was operated continuously for several months and although deterioration was observed visually, the source continued to produce ions at a rate similar that of the initial conditions. The results indicated that the DPIS may have a longer operating life than a conventional corona discharge.

Simultaneous imaging of multiple neurotransmitters and neuroactive substances in the brain by desorption electrospray ionization mass spectrometry.

Science.gov (United States)

Shariatgorji, Mohammadreza; Strittmatter, Nicole; Nilsson, Anna; Källback, Patrik; Alvarsson, Alexandra; Zhang, Xiaoqun; Vallianatou, Theodosia; Svenningsson, Per; Goodwin, Richard J A; Andren, Per E

2016-08-01

With neurological processes involving multiple neurotransmitters and neuromodulators, it is important to have the ability to directly map and quantify multiple signaling molecules simultaneously in a single analysis. By utilizing a molecular-specific approach, namely desorption electrospray ionization mass spectrometry imaging (DESI-MSI), we demonstrated that the technique can be used to image multiple neurotransmitters and their metabolites (dopamine, dihydroxyphenylacetic acid, 3-methoxytyramine, serotonin, glutamate, glutamine, aspartate, γ-aminobutyric acid, adenosine) as well as neuroactive drugs (amphetamine, sibutramine, fluvoxamine) and drug metabolites in situ directly in brain tissue sections. The use of both positive and negative ionization modes increased the number of identified molecular targets. Chemical derivatization by charge-tagging the primary amines of molecules significantly increased the sensitivity, enabling the detection of low abundant neurotransmitters and other neuroactive substances previously undetectable by MSI. The sensitivity of the imaging approach of neurochemicals has a great potential in many diverse applications in fields such as neuroscience, pharmacology, drug discovery, neurochemistry, and medicine. Copyright © 2016 Elsevier Inc. All rights reserved.

Electrospray ionization mass spectrometric method for the determination of cannabinoid precursors

DEFF Research Database (Denmark)

Hansen, H.H.; Hansen, S.H.; Bøjrnsdottir, I.

1999-01-01

electrospray ionization mass spectrometry (ESI-MS). The procedure provides complete positioning of all acyl and alkenyl groups contained in each NAPE species. The calibration curve for standard NAPE was linear over the range 100 fmol-50 pmol (0.1-50 ng) per injection. The lower limit of detection (signal......-to-noise ratio of 3) was 100 fmol, implying that this method is superior to previous methods for the determination of NAPE. These results suggest that this ESI-MS method can be used to identify and quantify NAPE species in mammalian tissues and provide information on the corresponding NAEs to be released from...

Improvement of ionizer and power supply of 860 A sputtering negative ion source

International Nuclear Information System (INIS)

An Kun; Yu Lingda; Wu Bingbing; Wang Guangfu

2014-01-01

A transmission surface type ionizer was developed with a φ2.5 mm stainless steel sheath core heating cable, and the ion source power supply was also improved. A continuous adjustable DC switching power supply was employed instead of the original AC power supply as the ionizer power supply, and a 0 - -20 kV DC power supply at the ground potential as the power of the immersion lens replaced the original 10 kV DC power supply suspended in -20 kV. The variation of the beam intensity of H"- in the front Faraday cup of the GIC4117 2 × 1.7 MV tandetron with the ionizer heating current was also shown. (authors)

Comprehensive biothreat cluster identification by PCR/electrospray-ionization mass spectrometry.

Directory of Open Access Journals (Sweden)

Rangarajan Sampath

Full Text Available Technology for comprehensive identification of biothreats in environmental and clinical specimens is needed to protect citizens in the case of a biological attack. This is a challenge because there are dozens of bacterial and viral species that might be used in a biological attack and many have closely related near-neighbor organisms that are harmless. The biothreat agent, along with its near neighbors, can be thought of as a biothreat cluster or a biocluster for short. The ability to comprehensively detect the important biothreat clusters with resolution sufficient to distinguish the near neighbors with an extremely low false positive rate is required. A technological solution to this problem can be achieved by coupling biothreat group-specific PCR with electrospray ionization mass spectrometry (PCR/ESI-MS. The biothreat assay described here detects ten bacterial and four viral biothreat clusters on the NIAID priority pathogen and HHS/USDA select agent lists. Detection of each of the biothreat clusters was validated by analysis of a broad collection of biothreat organisms and near neighbors prepared by spiking biothreat nucleic acids into nucleic acids extracted from filtered environmental air. Analytical experiments were carried out to determine breadth of coverage, limits of detection, linearity, sensitivity, and specificity. Further, the assay breadth was demonstrated by testing a diverse collection of organisms from each biothreat cluster. The biothreat assay as configured was able to detect all the target organism clusters and did not misidentify any of the near-neighbor organisms as threats. Coupling biothreat cluster-specific PCR to electrospray ionization mass spectrometry simultaneously provides the breadth of coverage, discrimination of near neighbors, and an extremely low false positive rate due to the requirement that an amplicon with a precise base composition of a biothreat agent be detected by mass spectrometry.

The production of ultra-thin layers of ion-exchange resin and metallic silver by electrospraying

International Nuclear Information System (INIS)

Wyllie, H.A.

1988-10-01

Highly efficient radioactive sources for use in radioisotope metrology have been prepared on ultra-thin layers of electrosprayed ion-exchange resin. The efficiency of these sources can be reduced for the purpose of radioactivity standardisation by coating them with conducting silver layers which are also produced by electrospraying. A description is given of improvements to the electrospraying methods, together with details of the rotating, oscillating source-mount turntable

Method Development for Binding Media Analysis in Painting Cross-Sections by Desorption Electrospray Ionization-Mass Spectrometry (DESI-MS).

Science.gov (United States)

Watts, Kristen; Lagalante, Anthony

2018-06-06

Art conservation science is in need of a relatively nondestructive way of rapidly identifying the binding media within a painting cross-section and isolating binding media to specific layers within the cross-section. Knowledge of the stratigraphy of cross-sections can be helpful for removing possible unoriginal paint layers on the artistic work. Desorption electrospray ionization-mass spectrometry (DESI-MS) was used in ambient mode to study cross-sections from mock-up layered paint samples and samples from a 17th century baroque painting. The DESI spray was raster scanned perpendicular to the cross-section layers to maximize lateral resolution then analyzed with a triple quadrupole mass analyzer in linear ion trap mode. From these scans, isobaric mass maps were created to map the locations of masses indicative of particular binding media onto the cross-sections. Line paint-outs of pigments in different binding media showed specific and unique ions to distinguish between the modern acrylic media and the lipid containing binding media. This included: OP (EO) 9 surfactant in positive ESI for acrylic (m/z 621), and oleic (m/z 281), stearic (m/z 283), and azelaic (m/z 187) acids in negative ESI for oil and egg tempera. DESI-MS maps of mock-up cross-sections of layered pigmented binding media showed correlation between these ions and the layers with a spatial resolution of 100 μm. DESI-MS is effective in monitoring binding media within an intact painting cross-section via mass spectrometric methods. This includes distinguishing between lipid-containing and modern binding materials present in a known mockup cross section matrix as well as identifying lipid binding media in a 17th century baroque era painting. This article is protected by copyright. All rights reserved.

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

Science.gov (United States)

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.

CHARACTERIZATION OF DANSYLATED CYSTEINE, GLUTATHIONE DISULFIDE, CYSTEINE AND CYSTINE BY NARROW BORE LIQUID CHROMATOGRAPHY/ELECTROSPRAY IONIZATION MASS SPECTROMETRY

Science.gov (United States)

A method using reversed phase high performance liquid chromatography/electrospray ionization-mass spectrometric (RP-LC/ESI-MS) method has been developed to confirm the identity of dansylated derivatives of cysteine and glutathione, and their respective dimers. Cysteine, GSH, CSSC...

Origin of supercharging in electrospray ionization of noncovalent complexes from aqueous solution.

Science.gov (United States)

Sterling, Harry J; Williams, Evan R

2009-10-01

The use of m-nitrobenzyl alcohol (m-NBA) to enhance charging of noncovalent complexes formed by electrospray ionization from aqueous solutions was investigated. Addition of up to 1% m-NBA can result in a significant increase in the average charging of complexes, ranging from approximately 13% for the homo-heptamer of NtrC4-RC (317 kDa; maximum charge state increases from 42+ to 44+) to approximately 49% for myoglobin (17.6 kDa; maximum charge state increases from 9+ to 16+). Charge state distributions of larger complexes obtained from heated solutions to which no m-NBA was added are remarkably similar to those containing small amounts of m-NBA. Dissociation of the complexes through identical channels both upon addition of higher concentrations of m-NBA and heating is observed. These results indicate that the enhanced charging upon addition of m-NBA to aqueous electrospray solutions is a result of droplet heating owing to the high boiling point of m-NBA, which results in a change in the higher-order structure and/or dissociation of the complexes. For monomeric proteins and small complexes, the enhancement of charging is lower for heated aqueous solutions than from solutions with m-NBA because rapid folding of proteins from heated solutions that do not contain m-NBA can occur after the electrospray droplet is formed and is evaporatively cooled.

Identification of Guest-Host Inclusion Complexes in the Gas Phase by Electrospray Ionization-Mass Spectrometry

Science.gov (United States)

Mendes, De´bora C.; Ramamurthy, Vaidhyanathan; Da Silva, Jose´ P.

2015-01-01

In this laboratory experiment, students follow a step-by-step procedure to prepare and study guest-host complexes in the gas phase using electrospray ionization-mass spectrometry (ESI-MS). Model systems are the complexes of hosts cucurbit[7]uril (CB7) and cucurbit[8]uril (CB8) with the guest 4-styrylpyridine (SP). Aqueous solutions of CB7 or CB8…

Loss of ions in cavity ionization chambers

International Nuclear Information System (INIS)

Takata, N.; Tran, N.T.; Kim, E.; Marsoem, P.; Kurosawa, T.; Koyama, Y.

2005-01-01

Ion losses due to initial recombination, volume recombination, and back diffusion were each determined by measurements and calculations for different size cylindrical ionization chambers and spherical ionization chambers. By measuring signal currents from these ionization chambers irradiated with 60 Co gamma rays, two groups of ion losses were obtained. (Group 1) Ion loss due to initial recombination and diffusion, which changes proportionally to the inverse of the voltage applied to the ionization chambers; (and group 2) ion loss due to volume recombination, which changes proportionally to the inverse of the square of the applied voltage. The diffusion loss was obtained separately by computing electric field distributions in the ionization chambers. It was found that diffusion loss is larger than initial recombination loss for the cylindrical ionization chambers and vise versa for the spherical ionization chambers

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

Science.gov (United States)

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...

Using precursor ion scan of 184 with liquid chromatography-electrospray ionization-tandem mass spectrometry for concentration normalization in cellular lipidomic studies.

Science.gov (United States)

Chao, Hsi-Chun; Chen, Guan-Yuan; Hsu, Lih-Ching; Liao, Hsiao-Wei; Yang, Sin-Yu; Wang, San-Yuan; Li, Yu-Liang; Tang, Sung-Chun; Tseng, Yufeng Jane; Kuo, Ching-Hua

2017-06-08

Cellular lipidomic studies have been favored approaches in many biomedical research areas. To provide fair comparisons of the studied cells, it is essential to perform normalization of the determined concentration before lipidomic analysis. This study proposed a cellular lipidomic normalization method by measuring the phosphatidylcholine (PC) and sphingomyelin (SM) contents in cell extracts. To provide efficient analysis of PC and SM in cell extracts, flow injection analysis-electrospray ionization-tandem mass spectrometry (FIA-ESI-MS/MS) with a precursor ion scan (PIS) of m/z 184 was used, and the parameters affecting the performance of the method were optimized. Good linearity could be observed between the cell extract dilution factor and the reciprocal of the total ion chromatogram (TIC) area in the PIS of m/z 184 within the dilution range of 1- to 16-fold (R 2  = 0.998). The calibration curve could be used for concentration adjustment of the unknown concentration of a cell extract. The intraday and intermediate precisions were below 10%. The accuracy ranged from 93.0% to 105.6%. The performance of the new normalization method was evaluated using different numbers of HCT-116 cells. Sphingosine, ceramide (d18:1/18:0), SM (d18:1/18:0) and PC (16:1/18:0) were selected as the representative test lipid species, and the results showed that the peak areas of each lipid species obtained from different cell numbers were within a 20% variation after normalization. Finally, the PIS of 184 normalization method was applied to study ischemia-induced neuron injury using oxygen and glucose deprivation (OGD) on primary neuronal cultured cells. Our results showed that the PIS of 184 normalization method is an efficient and effective approach for concentration normalization in cellular lipidomic studies. Copyright © 2017 Elsevier B.V. All rights reserved.

CHARACTERIZATION OF DANSYLATED CYSTEINE, CYSTINE, GLUTATHIONE, AND GLUTATHIONE DISULFIDE BY NARROW BORE LIQUID CHROMATOGRAPHY - ELECTROSPRAY IONIZATION MASS SPECTROMETRY

Science.gov (United States)

A method using reversed phase high performance liquid chromtography/electrospray ionization-mass spectrometry (RP-LC/ESI-MS) has been developed to confirm the dientity of dansylated derivatives of cysteine (C) and glutathione (GSH), and their respective dimers, cystine (CSSC) and...

A new ultrahigh performance liquid chromatography with diode array detection coupled to electrospray ionization and quadrupole time-of-flight mass spectrometry analytical strategy for fast analysis and improved characterization of phenolic compounds in apple products.

Science.gov (United States)

Ramirez-Ambrosi, M; Abad-Garcia, B; Viloria-Bernal, M; Garmon-Lobato, S; Berrueta, L A; Gallo, B

2013-11-05

A new, rapid, selective and sensitive ultrahigh performance liquid chromatography with diode array detection coupled to electrospray ionization and quadrupole time-of-flight mass spectrometry (UHPLC-DAD-ESI-Q-ToF-MS) strategy using automatic and simultaneous acquisition of exact mass at high and low collision energy, MS(E), has been developed to obtain polyphenolic profile of apples, apple pomace and apple juice from Asturian cider apples in a single run injection of 22 min. MS(E) spectral data acquisition overcomes chromatographic co-elution problems, performing simultaneous collection of precursor ions as well as other ions produced as a result of their fragmentation, which allows resolving complex spectra from mixtures of precursor ions in an unsupervised way and eases their interpretation. Using this technique, 52 phenolic compounds of five different classes were readily characterized in these apple extracts in both positive and negative ionization modes. The spectral data for phenolic compounds obtained using this acquisition mode are comparable to those obtained by conventional LC-MS/MS as exemplified in this work. Among the 52 phenolic compounds identified in this work, 2 dihydrochalcones and 3 flavonols have been tentatively identified for the first time in apple products. Moreover, 2 flavanols, 4 dihydrochalcones, 9 hydroxycinnamic acids and 4 flavonols had not been previously reported in apple by ToF analysis to our knowledge. Copyright © 2013 Elsevier B.V. All rights reserved.

Surface ionization ion source with high current

International Nuclear Information System (INIS)

Fang Jinqing; Lin Zhizhou; Yu Lihua; Zhan Rongan; Huang Guojun; Wu Jianhua

1986-04-01

The working principle and structure of a surface ionization ion source with high current is described systematically. Some technological keypoints of the ion source are given in more detail, mainly including: choosing and shaping of the material of the surface ionizer, heating of the ionizer, distributing of working vapour on the ionizer surface, the flow control, the cooling problem at the non-ionization surface and the ion optics, etc. This ion source has been used since 1972 in the electromagnetic isotope separator with 180 deg angle. It is suitable for separating isotopes of alkali metals and rare earth metals. For instance, in the case of separating Rubidium, the maximum ion current of Rbsup(+) extracted from the ion source is about 120 mA, the maximum ion current accepted by the receiver is about 66 mA, the average ion current is more than 25 mA. The results show that our ion source have advantages of high ion current, good characteristics of focusing ion beam, working stability and structure reliability etc. It may be extended to other fields. Finally, some interesting phenomena in the experiment are disccused briefly. Some problems which should be investigated are further pointed out

Accurate and rapid modeling of iron-bleomycin-induced DNA damage using tethered duplex oligonucleotides and electrospray ionization ion trap mass spectrometric analysis.

Science.gov (United States)

Harsch, A; Marzilli, L A; Bunt, R C; Stubbe, J; Vouros, P

2000-05-01

Bleomycin B(2)(BLM) in the presence of iron [Fe(II)] and O(2)catalyzes single-stranded (ss) and double-stranded (ds) cleavage of DNA. Electrospray ionization ion trap mass spectrometry was used to monitor these cleavage processes. Two duplex oligonucleotides containing an ethylene oxide tether between both strands were used in this investigation, allowing facile monitoring of all ss and ds cleavage events. A sequence for site-specific binding and cleavage by Fe-BLM was incorporated into each analyte. One of these core sequences, GTAC, is a known hot-spot for ds cleavage, while the other sequence, GGCC, is a hot-spot for ss cleavage. Incubation of each oligo-nucleotide under anaerobic conditions with Fe(II)-BLM allowed detection of the non-covalent ternary Fe-BLM/oligonucleotide complex in the gas phase. Cleavage studies were then performed utilizing O(2)-activated Fe(II)-BLM. No work-up or separation steps were required and direct MS and MS/MS analyses of the crude reaction mixtures confirmed sequence-specific Fe-BLM-induced cleavage. Comparison of the cleavage patterns for both oligonucleotides revealed sequence-dependent preferences for ss and ds cleavages in accordance with previously established gel electrophoresis analysis of hairpin oligonucleotides. This novel methodology allowed direct, rapid and accurate determination of cleavage profiles of model duplex oligonucleotides after exposure to activated Fe-BLM.

Petroleomics by electrospray ionization FT-ICR mass spectrometry coupled to partial least squares with variable selection methods: prediction of the total acid number of crude oils.

Science.gov (United States)

Terra, Luciana A; Filgueiras, Paulo R; Tose, Lílian V; Romão, Wanderson; de Souza, Douglas D; de Castro, Eustáquio V R; de Oliveira, Mirela S L; Dias, Júlio C M; Poppi, Ronei J

2014-10-07

Negative-ion mode electrospray ionization, ESI(-), with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was coupled to a Partial Least Squares (PLS) regression and variable selection methods to estimate the total acid number (TAN) of Brazilian crude oil samples. Generally, ESI(-)-FT-ICR mass spectra present a power of resolution of ca. 500,000 and a mass accuracy less than 1 ppm, producing a data matrix containing over 5700 variables per sample. These variables correspond to heteroatom-containing species detected as deprotonated molecules, [M - H](-) ions, which are identified primarily as naphthenic acids, phenols and carbazole analog species. The TAN values for all samples ranged from 0.06 to 3.61 mg of KOH g(-1). To facilitate the spectral interpretation, three methods of variable selection were studied: variable importance in the projection (VIP), interval partial least squares (iPLS) and elimination of uninformative variables (UVE). The UVE method seems to be more appropriate for selecting important variables, reducing the dimension of the variables to 183 and producing a root mean square error of prediction of 0.32 mg of KOH g(-1). By reducing the size of the data, it was possible to relate the selected variables with their corresponding molecular formulas, thus identifying the main chemical species responsible for the TAN values.

Effect of negative air ions on the potential for bacterial contamination of plastic medical equipment.

Science.gov (United States)

Shepherd, Simon J; Beggs, Clive B; Smith, Caroline F; Kerr, Kevin G; Noakes, Catherine J; Sleigh, P Andrew

2010-04-12

In recent years there has been renewed interest in the use of air ionizers to control the spread of infection in hospitals and a number of researchers have investigated the biocidal action of ions in both air and nitrogen. By comparison, the physical action of air ions on bacterial dissemination and deposition has largely been ignored. However, there is clinical evidence that air ions might play an important role in preventing the transmission of Acinetobacter infection. Although the reasons for this are unclear, it is hypothesized that a physical effect may be responsible: the production of air ions may negatively charge items of plastic medical equipment so that they repel, rather than attract, airborne bacteria. By negatively charging both particles in the air and items of plastic equipment, the ionizers minimize electrostatic deposition on these items. In so doing they may help to interrupt the transmission of Acinetobacter infection in certain healthcare settings such as intensive care units. A study was undertaken in a mechanically ventilated room under ambient conditions to accurately measure changes in surface potential exhibited by items of plastic medical equipment in the presence of negative air ions. Plastic items were suspended on nylon threads, either in free space or in contact with a table surface, and exposed to negative ions produced by an air ionizer. The charge build-up on the specimens was measured using an electric field mill while the ion concentration in the room air was recorded using a portable ion counter. The results of the study demonstrated that common items of equipment such as ventilator tubes rapidly developed a large negative charge (i.e. generally >-100V) in the presence of a negative air ionizer. While most items of equipment tested behaved in a similar manner to this, one item, a box from a urological collection and monitoring system (the only item made from styrene acrylonitrile), did however develop a positive charge in the

Effect of negative air ions on the potential for bacterial contamination of plastic medical equipment

Directory of Open Access Journals (Sweden)

Kerr Kevin G

2010-04-01

Full Text Available Abstract Background In recent years there has been renewed interest in the use of air ionizers to control the spread of infection in hospitals and a number of researchers have investigated the biocidal action of ions in both air and nitrogen. By comparison, the physical action of air ions on bacterial dissemination and deposition has largely been ignored. However, there is clinical evidence that air ions might play an important role in preventing the transmission of Acinetobacter infection. Although the reasons for this are unclear, it is hypothesized that a physical effect may be responsible: the production of air ions may negatively charge items of plastic medical equipment so that they repel, rather than attract, airborne bacteria. By negatively charging both particles in the air and items of plastic equipment, the ionizers minimize electrostatic deposition on these items. In so doing they may help to interrupt the transmission of Acinetobacter infection in certain healthcare settings such as intensive care units. Methods A study was undertaken in a mechanically ventilated room under ambient conditions to accurately measure changes in surface potential exhibited by items of plastic medical equipment in the presence of negative air ions. Plastic items were suspended on nylon threads, either in free space or in contact with a table surface, and exposed to negative ions produced by an air ionizer. The charge build-up on the specimens was measured using an electric field mill while the ion concentration in the room air was recorded using a portable ion counter. Results The results of the study demonstrated that common items of equipment such as ventilator tubes rapidly developed a large negative charge (i.e. generally >-100V in the presence of a negative air ionizer. While most items of equipment tested behaved in a similar manner to this, one item, a box from a urological collection and monitoring system (the only item made from styrene

Confirmatory analysis method for zeranol, its metabolites and related mycotoxins in urine by liquid chromatography-negative ion electrospray tandem mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Bennekom, E.O. van; Brouwer, L.; Laurant, E.H.M.; Hooijerink, H.; Nielen, M.W.F

2002-11-25

The determination of the banned anabolic substance zeranol and the metabolites taleranol and zearalanone in bovine urine is complicated by the occurrence of the structurally-related mycotoxin zearalenone and the corresponding {alpha}- and {beta}-zearalenol metabolites which possess similar estrogenic properties. A liquid chromatography-negative ion electrospray tandem mass spectrometric method is presented for the confirmatory analysis of all six resorcylic acid lactones ('zeranols') in urine samples using deuterium-labelled internal standards. The method was validated as a confirmatory method for bovine urine samples according to new draft EU guidelines and showed good precision and linearity, and CC{alpha} and CC{beta} values of 0.02-0.30 and <1.0 ng ml{sup -1}, respectively. The applicability was demonstrated by comparing the results of an incurred sample with previous results on the same sample obtained by gas chromatography high resolution mass spectrometry. Preliminary data show that following a simple matrix solid phase dispersion clean-up, liver samples from poultry will be amenable to this method as well.

The technique of negative ions in mass spectrometry. Application to aromatics

International Nuclear Information System (INIS)

George, G.

1984-01-01

The author examines the application of NCI (study of negative ions created by chemical ionization and particularly by a reacting negative ion) on a model popular at the present time: the passion fruit. The author stresses that this technique has its limitations and should be considered as auxiliary to electron impact. However, it seems destined for a promising future for the analysis of natural produce [fr

Simultaneous determination of clebopride and a major metabolite N-desbenzylclebopride in plasma by capillary gas chromatography-negative-ion chemical ionization mass spectrometry.

Science.gov (United States)

Robinson, P R; Jones, M D; Maddock, J; Rees, L W

1991-03-08

A procedure for the simultaneous assay of clebopride and its major metabolite N-desbenzylclebopride in plasma has been developed. The method utilizes capillary gas chromatography-negative-ion chemical ionization mass spectrometry with selected-ion monitoring of characteristic ions. Employing 2-ethoxy analogues as internal standards, the benzamides were extracted from basified plasma using dichloromethane. Subsequent reaction with heptafluorobutyric anhydride produced volatile mono- and diheptafluorobutyryl derivatives of clebopride and N-desbenzylclebopride, respectively. The methane negative-ion mass spectra of these derivatives exhibited intense high-mass ions ideal for specific quantitation of low levels in biological fluids. Using this procedure the recovery of the drug and metabolite from human plasma was found to be 84.4 +/- 1.5% (n = 3) and 77.4 +/- 4.7% (n = 3), respectively, at 0.5 ng/ml. Measurement of both compounds down to 0.10 ng/ml with a coefficient of variation of less than 10.5% is described. Plasma levels are reported in four volunteers up to 24 h following oral administration of 1 mg of clebopride malate salt.

Charge State Coalescence During Electrospray Ionization Improves Peptide Identification by Tandem Mass Spectrometry

Science.gov (United States)

Meyer, Jesse G.; A. Komives, Elizabeth

2012-08-01

We report the effects of supercharging reagents dimethyl sulphoxide (DMSO) and m-nitrobenzyl alcohol ( m-NBA) applied to untargeted peptide identification, with special emphasis on non-tryptic peptides. Peptides generated from a mixture of five standard proteins digested with trypsin, elastase, or pepsin were separated with nanoflow liquid chromatography using mobile phases modified with either 5 % DMSO or 0.1 % m-NBA. Eluting peptides were ionized by online electrospray and sequenced by both CID and ETD using data-dependent MS/MS. Statistically significant improvements in peptide identifications were observed with DMSO co-solvent. In order to understand this observation, we assessed the effects of supercharging reagents on the chromatographic separation and the electrospray quality. The increase in identifications was not due to supercharging, which was greater for the 0.1 % m-NBA co-solvent and not observed for the 5.0 % DMSO co-solvent. The improved MS/MS efficiency using the DMSO modified mobile phase appeared to result from charge state coalescence.

Gas-phase reaction rate constants for atmospheric pressure ionization in ion-mobility spectrometry

International Nuclear Information System (INIS)

Vandiver, V.J.

1987-01-01

Ion-mobility spectrometry (IMS) is an instrumental technique in which gaseous ions are formed from neutral molecules by proton and charge transfer from reactant ions through collisional ionization. An abbreviated rate theory has been proposed for atmospheric pressure ionization (API) in IMS, but supporting experimental measurements have not been reported. The objectives of this thesis were (1) assessment of existing API rate theory using positive and negative product ions in IMS, (2) measurement of API equilibria and kinetics for binary mixtures, and (3) investigating of cross-ionizations with multiple-product ions in API reactions. Although IMS measurements and predictions from rate theory were comparable, shapes and slopes of response curves for both proton transfer and electron capture were not described exactly by existing theory. In particular, terms that are needed for calculation of absolute rate constants were unsuitable in the existing theory. These included recombination coefficients,initial number of reactant ions, and opposing ion densities

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

Energy Technology Data Exchange (ETDEWEB)

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.

Assignment by Negative-Ion Electrospray Tandem Mass Spectrometry of the Tetrasaccharide Backbones of Monosialylated Glycans Released from Bovine Brain Gangliosides

Science.gov (United States)

Chai, Wengang; Zhang, Yibing; Mauri, Laura; Ciampa, Maria G.; Mulloy, Barbara; Sonnino, Sandro; Feizi, Ten

2018-05-01

Gangliosides, as plasma membrane-associated sialylated glycolipids, are antigenic structures and they serve as ligands for adhesion proteins of pathogens, for toxins of bacteria, and for endogenous proteins of the host. The detectability by carbohydrate-binding proteins of glycan antigens and ligands on glycolipids can be influenced by the differing lipid moieties. To investigate glycan sequences of gangliosides as recognition structures, we have underway a program of work to develop a "gangliome" microarray consisting of isolated natural gangliosides and neoglycolipids (NGLs) derived from glycans released from them, and each linked to the same lipid molecule for arraying and comparative microarray binding analyses. Here, in the first phase of our studies, we describe a strategy for high-sensitivity assignment of the tetrasaccharide backbones and application to identification of eight of monosialylated glycans released from bovine brain gangliosides. This approach is based on negative-ion electrospray mass spectrometry with collision-induced dissociation (ESI-CID-MS/MS) of the desialylated glycans. Using this strategy, we have the data on backbone regions of four minor components among the monosialo-ganglioside-derived glycans; these are of the ganglio-, lacto-, and neolacto-series.

Negative ion sources

International Nuclear Information System (INIS)

Ishikawa, Junzo; Takagi, Toshinori

1983-01-01

Negative ion sources have been originally developed at the request of tandem electrostatic accelerators, and hundreds of nA to several μA negative ion current has been obtained so far for various elements. Recently, the development of large current hydrogen negative ion sources has been demanded from the standpoint of the heating by neutral particle beam injection in nuclear fusion reactors. On the other hand, the physical properties of negative ions are interesting in the thin film formation using ions. Anyway, it is the present status that the mechanism of negative ion action has not been so fully investigated as positive ions because the history of negative ion sources is short. In this report, the many mechanisms about the generation of negative ions proposed so far are described about negative ion generating mechanism, negative ion source plasma, and negative ion generation on metal surfaces. As a result, negative ion sources are roughly divided into two schemes, plasma extraction and secondary ion extraction, and the former is further classified into the PIG ion source and its variation and Duoplasmatron and its variation; while the latter into reflecting and sputtering types. In the second half of the report, the practical negative ion sources of each scheme are described. If the mechanism of negative ion generation will be investigated more in detail and the development will be continued under the unified know-how as negative ion sources in future, the development of negative ion sources with which large current can be obtained for any element is expected. (Wakatsuki, Y.)

Increasing Protein Charge State When Using Laser Electrospray Mass Spectrometry

Science.gov (United States)

Karki, Santosh; Flanigan, Paul M.; Perez, Johnny J.; Archer, Jieutonne J.; Levis, Robert J.

2015-05-01

Femtosecond (fs) laser vaporization is used to transfer cytochrome c, myoglobin, lysozyme, and ubiquitin from the condensed phase into an electrospray (ES) plume consisting of a mixture of a supercharging reagent, m-nitrobenzyl alcohol ( m-NBA), and trifluoroacetic acid (TFA), acetic acid (AA), or formic acid (FA). Interaction of acid-sensitive proteins like cytochrome c and myoglobin with the highly charged ES droplets resulted in a shift to higher charge states in comparison with acid-stable proteins like lysozyme and ubiquitin. Laser electrospray mass spectrometry (LEMS) measurements showed an increase in both the average charge states (Zavg) and the charge state with maximum intensity (Zmode) for acid-sensitive proteins compared with conventional electrospray ionization mass spectrometry (ESI-MS) under equivalent solvent conditions. A marked increase in ion abundance of higher charge states was observed for LEMS in comparison with conventional electrospray for cytochrome c (ranging from 19+ to 21+ versus 13+ to 16+) and myoglobin (ranging from 19+ to 26+ versus 18+ to 21+) using an ES solution containing m-NBA and TFA. LEMS measurements as a function of electrospray flow rate yielded increasing charge states with decreasing flow rates for cytochrome c and myoglobin.

Subtle differences in molecular recognition between modified glycopeptide antibiotics and bacterial receptor peptides identified by electrospray ionization mass spectrometry

DEFF Research Database (Denmark)

Jørgensen, Thomas J. D.; Staroske, T; Roepstorff, P

1999-01-01

showing that electrospray ionization mass spectrometry (ESI-MS) can be used in the rapid quantitative analysis of mixtures of vancomycin-group antibiotics and their bacterial cell-wall receptors allowing the identification of even subtle differences in binding constants. Differences in affinities...

Differentiation of oral bacteria in in vitro cultures and human saliva by secondary electrospray ionization - mass spectrometry

Science.gov (United States)

Bregy, Lukas; Müggler, Annick R.; Martinez-Lozano Sinues, Pablo; García-Gómez, Diego; Suter, Yannick; Belibasakis, Georgios N.; Kohler, Malcolm; Schmidlin, Patrick R.; Zenobi, Renato

2015-10-01

The detection of bacterial-specific volatile metabolites may be a valuable tool to predict infection. Here we applied a real-time mass spectrometric technique to investigate differences in volatile metabolic profiles of oral bacteria that cause periodontitis. We coupled a secondary electrospray ionization (SESI) source to a commercial high-resolution mass spectrometer to interrogate the headspace from bacterial cultures and human saliva. We identified 120 potential markers characteristic for periodontal pathogens Aggregatibacter actinomycetemcomitans (n = 13), Porphyromonas gingivalis (n = 70), Tanerella forsythia (n = 30) and Treponema denticola (n = 7) in in vitro cultures. In a second proof-of-principle phase, we found 18 (P. gingivalis, T. forsythia and T. denticola) of the 120 in vitro compounds in the saliva from a periodontitis patient with confirmed infection with P. gingivalis, T. forsythia and T. denticola with enhanced ion intensity compared to two healthy controls. In conclusion, this method has the ability to identify individual metabolites of microbial pathogens in a complex medium such as saliva.

Salinity and solvent effects on the characterization of naphthenic acids from Athabasca oil sands using electrospray ionization

International Nuclear Information System (INIS)

Headley, J.; Peru, K.; Barrow, M.; Derrick, P.

2010-01-01

This study investigated the salinity and solvent effects on the characterization of naphthenic acids (NA) in oil sands. The mass spectra of NA were obtained using an electrospray ionization method combined with a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The study showed that while monocarboxylic compounds (C n H 2n+z O 2 ) in the z=-4, -6, and -12 of the 2,3 and 6-ring NA in the carbon number range of 13 to 19 were prevalent in the dichloromethane and acetonitrile co-solvent systems, the addition of salt resulted in a reduction of the observed species, the complete elimination of dicarboxylic acids, and an 80 per cent reduction in O 3 species with similar carbon number range and z values. The dicarboxylic acids were also less toxic than monocarboxylic acids. Results of the study will be used to refine methods of remediating oil sands and process water contaminated soils.

Mechanistic and Kinetic Study of Singlet O2 Oxidation of Methionine by On-Line Electrospray Ionization Mass Spectrometry.

Science.gov (United States)

Liu, Fangwei; Lu, Wenchao; Yin, Xunlong; Liu, Jianbo

2016-01-01

We report a reaction apparatus developed to monitor singlet oxygen ((1)O2) reactions in solution using on-line ESI mass spectrometry and spectroscopy measurements. (1)O2 was generated in the gas phase by the reaction of H2O2 with Cl2, detected by its emission at 1270 nm, and bubbled into aqueous solution continuously. (1)O2 concentrations in solution were linearly related to the emission intensities of airborne (1)O2, and their absolute scales were established based on a calibration using 9,10-anthracene dipropionate dianion as an (1)O2 trapping agent. Products from (1)O2 oxidation were monitored by UV-Vis absorption and positive/negative ESI mass spectra, and product structures were elucidated using collision-induced dissociation-tandem mass spectrometry. To suppress electrical discharge in negative ESI of aqueous solution, methanol was added to electrospray via in-spray solution mixing using theta-glass ESI emitters. Capitalizing on this apparatus, the reaction of (1)O2 with methionine was investigated. We have identified methionine oxidation intermediates and products at different pH, and measured reaction rate constants. (1)O2 oxidation of methionine is mediated by persulfoxide in both acidic and basic solutions. Persulfoxide continues to react with another methionine, yielding methionine sulfoxide as end-product albeit with a much lower reaction rate in basic solution. Density functional theory was used to explore reaction potential energy surfaces and establish kinetic models, with solvation effects simulated using the polarized continuum model. Combined with our previous study of gas-phase methionine ions with (1)O2, evolution of methionine oxidation pathways at different ionization states and in different media is described.

Chemical ionization mass spectrometry of indol-3yl-acetic acid and cis-abscisic acid: evaluation of negative ion detection and quantification of cis-abscisic acid in growing maize roots

International Nuclear Information System (INIS)

Rivier, L.; Saugy, M.

1986-01-01

Mass spectra of the derivatives of indol-3yl-acetic acid and cis-abscisic acid were obtained in electron impact and chemical ionization positive ion and negative ion modes. The respective merits of methane, isobutane, and ammonia as reagent gases for structure determination and sensitive detection were compared using the methyl esters. From one to 10 fluorine atoms were attached to IAA to improve the electron-capturing properties of the molecule. The best qualitative information was obtained when using positive ion chemical ionization with methane. However, the most sensitive detection, with at least two ions per molecule, was achieved by electron impact on the IAA-HFB-ME derivative and by negative ion chemical ionization with NH 3 on the ABA-methyl ester derivative. p ]Quantitative analyses of ABA in different parts of maize (Zea mays cv. LG 11) root tips were performed by the latter technique. It was found that the cap and apex contained less ABA than the physiologically older parts of the root such as the elongation zone and the more differentiated tissues. This technique was also used to show a relation between maize root growth and the endogenous ABA level of the elongation zone and root tip: there is more ABA in the slowly growing roots than in the rapidly growing ones. (author)

Using positive-ion electrospray ionization mass spectrometry and H/D exchange study phosphoryl group transfer reactions involved in amino acid ester isopropyl phosphoramidates of Brefeldin A

International Nuclear Information System (INIS)

Fang, Mei-Juan; Zhang, He; Liao, Chao; Qiu, Ying-Kun; Fang, Hua; Zheng, Zhen-Yu; Gao, Xiang; Zhao, Yu-Fen; Wu, Zhen

2015-01-01

Highlights: • ESI-MS n , HRMS and H/D exchange were used. • The fragmentation pathways of NPAAE-BFA in ESI-MS n were described. • Fragment ions involved in phosphorus group’s rearrangement reactions were observed. • Two rearrangement mechanisms about phosphorylation–dephosphorylation were proposed. - Abstract: As mini-chemical models, amino acid ester isopropyl phosphoramidates of Brefeldin A (compounds 2a–2d) were synthesized and investigated by electrospray ionization tandem mass spectrometry in combination with H/D exchange. To further confirm the fragments’s structures, off-line Fourier transform resonance tandem mass spectrometry (FT-ICR-MS/MS) was also performed. The fragmentation rules of compounds 2a–2d have been summarized and the plausible schemes for the fragmentation pathways were proposed. In this study, one dephosphorylated ion and two phosphorylated ions were observed in ESI-MS 2 spectra of [M + Na] + ions for compounds 2a–2d. The possible mechanisms about phosphorylation and dephosphorylation were proposed and confirmed by H/D exchange. For the “dephosphorylation” rearrangement, a nitrogen atom was migrated from the phosphoryl group to the carbon atom of Brefeldin A’s backbone with losing a molecule of C 3 H 7 PO 3 (122 Da). For the “phosphorylation” rearrangement, an oxygen atom of one phosphoryl group attacked the sideward phosphorus atom to form a nine-member ring intermediate, then two steps of C-H covalent bond cleavage with consecutive migration of hydrogen atom to lose a molecule of C 16 H 20 O 2 (244 Da). The two proposed rearrangement mechanisms about phosphoryl group transfer might be valuable for the structure analysis of other analogs and provide insights into elucidating the dynamic process of the phosphorylation–dephosphorylation of proteins

Using positive-ion electrospray ionization mass spectrometry and H/D exchange study phosphoryl group transfer reactions involved in amino acid ester isopropyl phosphoramidates of Brefeldin A

Energy Technology Data Exchange (ETDEWEB)

Fang, Mei-Juan; Zhang, He; Liao, Chao; Qiu, Ying-Kun [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); Fang, Hua [The Third Institute of Oceanography of the State Oceanic Administration, Xiamen 361005 (China); Zheng, Zhen-Yu [College of Chemistry and Chemical Engineering, Department of Chemistry, Xiamen University, Xiamen 361005 (China); Gao, Xiang [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); Zhao, Yu-Fen [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); College of Chemistry and Chemical Engineering, Department of Chemistry, Xiamen University, Xiamen 361005 (China); Wu, Zhen, E-mail: wuzhen@xmu.edu.cn [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China)

2015-01-01

Highlights: • ESI-MS{sup n}, HRMS and H/D exchange were used. • The fragmentation pathways of NPAAE-BFA in ESI-MS{sup n} were described. • Fragment ions involved in phosphorus group’s rearrangement reactions were observed. • Two rearrangement mechanisms about phosphorylation–dephosphorylation were proposed. - Abstract: As mini-chemical models, amino acid ester isopropyl phosphoramidates of Brefeldin A (compounds 2a–2d) were synthesized and investigated by electrospray ionization tandem mass spectrometry in combination with H/D exchange. To further confirm the fragments’s structures, off-line Fourier transform resonance tandem mass spectrometry (FT-ICR-MS/MS) was also performed. The fragmentation rules of compounds 2a–2d have been summarized and the plausible schemes for the fragmentation pathways were proposed. In this study, one dephosphorylated ion and two phosphorylated ions were observed in ESI-MS{sup 2} spectra of [M + Na]{sup +} ions for compounds 2a–2d. The possible mechanisms about phosphorylation and dephosphorylation were proposed and confirmed by H/D exchange. For the “dephosphorylation” rearrangement, a nitrogen atom was migrated from the phosphoryl group to the carbon atom of Brefeldin A’s backbone with losing a molecule of C{sub 3}H{sub 7}PO{sub 3} (122 Da). For the “phosphorylation” rearrangement, an oxygen atom of one phosphoryl group attacked the sideward phosphorus atom to form a nine-member ring intermediate, then two steps of C-H covalent bond cleavage with consecutive migration of hydrogen atom to lose a molecule of C{sub 16}H{sub 20}O{sub 2} (244 Da). The two proposed rearrangement mechanisms about phosphoryl group transfer might be valuable for the structure analysis of other analogs and provide insights into elucidating the dynamic process of the phosphorylation–dephosphorylation of proteins.

Pulsed voltage electrospray ion source and method for preventing analyte electrolysis

Science.gov (United States)

Kertesz, Vilmos [Knoxville, TN; Van Berkel, Gary [Clinton, TN

2011-12-27

An electrospray ion source and method of operation includes the application of pulsed voltage to prevent electrolysis of analytes with a low electrochemical potential. The electrospray ion source can include an emitter, a counter electrode, and a power supply. The emitter can include a liquid conduit, a primary working electrode having a liquid contacting surface, and a spray tip, where the liquid conduit and the working electrode are in liquid communication. The counter electrode can be proximate to, but separated from, the spray tip. The power system can supply voltage to the working electrode in the form of a pulse wave, where the pulse wave oscillates between at least an energized voltage and a relaxation voltage. The relaxation duration of the relaxation voltage can range from 1 millisecond to 35 milliseconds. The pulse duration of the energized voltage can be less than 1 millisecond and the frequency of the pulse wave can range from 30 to 800 Hz.

Specific determination of 20 primary aromatic amines in aqueous food simulants by liquid chromatography-electrospray ionization-tandem mass spectrometry

DEFF Research Database (Denmark)

Mortensen, Sarah Kelly; Trier, Xenia Thorsager; Foverskov, Annie

2005-01-01

A multi-analyte method without any pre-treatment steps using reversed-phase liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) was developed and applied for the determination of 20 primary aromatic amines (PAA) associated with polyurethane (PUR) products or azo...

Infrared laser dissociation of single megadalton polymer ions in a gated electrostatic ion trap: the added value of statistical analysis of individual events.

Science.gov (United States)

Halim, Mohammad A; Clavier, Christian; Dagany, Xavier; Kerleroux, Michel; Dugourd, Philippe; Dunbar, Robert C; Antoine, Rodolphe

2018-05-07

In this study, we report the unimolecular dissociation mechanism of megadalton SO 3 -containing poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) polymer cations and anions with the aid of infrared multiphoton dissociation coupled to charge detection ion trap mass spectrometry. A gated electrostatic ion trap ("Benner trap") is used to store and detect single gaseous polymer ions generated by positive and negative polarity in an electrospray ionization source. The trapped ions are then fragmented due to the sequential absorption of multiple infrared photons produced from a continuous-wave CO 2 laser. Several fragmentation pathways having distinct signatures are observed. Highly charged parent ions characteristically adopt a distinctive "stair-case" pattern (assigned to the "fission" process) whereas low charge species take on a "funnel like" shape (assigned to the "evaporation" process). Also, the log-log plot of the dissociation rate constants as a function of laser intensity between PAMPS positive and negative ions is significantly different.

Production techniques for rare earth and other heavy negative ions

International Nuclear Information System (INIS)

McK Hyder, H.R.; Ashenfelter, J.; McGrath, R.

1998-01-01

Current nuclear structure studies demand a wide range of heavy negative ion beams for tandem acceleration. Some of the wanted isotopes have low natural abundances and many have low or negative electron affinities. For these, gas injection or the use of hydrides, oxides, or fluorides is required to achieve usable intensities. The chemical properties of the target materials, and of the additive gases used to form molecular ions, often have detrimental effects on ion source performance and life. These effects include insulator breakdown, ionizer poisoning, and the erosion or deposition of material on critical electrodes. Methods of controlling sputter source conditions are being studied on the Wright Nuclear Structure Laboratory ion source test bench with the object of extending source life, increasing target efficiency, and achieving consistent negative ion outputs. Results are reported for several heavy ions including tellurium, neodymium, and ytterbium. copyright 1998 American Institute of Physics

Hyphenation of capillary high-performance ion-exchange chromatography with mass spectrometry using sheath-flow electrospray ionization.

Science.gov (United States)

Kochmann, Sven; Matysik, Frank-Michael

2014-12-15

Mass spectrometry (MS) is an attractive method for extending capillary-size ion chromatography (cHPIC) to create a valuable technique for speciation analysis. For hyphenation, the aqueous effluent of cHPIC has to be transformed into a volatile mixture for MS while preserving analytical concentrations as well as peak shapes during transfer from cHPIC to MS. Finally, the approach should technically be flexible and easy-to-use. A combination of cHPIC and sheath-flow electrospray ionization (ESI)-MS offers to solve all these challenges. cHPIC/sheath-flow-ESI-TOFMS was used in this study for the speciation analysis of various arsenic model compounds. These model compounds were analyzed with different hyphenation setups and configurations of cHPIC/MS and their respective assets and drawbacks were examined and discussed. The parameters (flow rate and composition of sheath liquid) of sheath-flow ESI and their influence on the performance of the spray and the sensitivity of the detector were investigated and compared with those of sheathless ESI. Using an injection valve to couple cHPIC and MS was found to be the best method for hyphenation, since it constitutes a flexible and dead-volume-free approach. The investigation of sheath-flow ESI revealed that the flow rate of the sheath liquid has to resemble the flow rate of the IC effluent to ensure a stable spray and that a composition of 2-propanol/water/ammonia at 50:50:0.2 (v/v/v) suits most applications without unilaterally promoting the sensitivity for either organic or inorganic compounds. The optimized setup and conditions were successfully applied to the analysis of a mixture of important arsenic species and used to determine limits of detection of organic and inorganic arsenic species (3.7 µg L(-1) elemental arsenic). A method for cHPIC/sheath-flow-ESI-MS was developed. The method was shown to be a valuable tool for speciation and trace analysis. It features no dead volume, fast transfer from IC to MS, only minimal

Interactions of nucleobases with alkali earth metal cations--electrospray ionization mass spectrometric study.

Science.gov (United States)

Frańska, Magdalena

2007-01-01

Interactions of nucleobases with alkali earth metal cations have been studied by electrospray ionization mass spectrometry (ESI-MS). Nucleobases containing at least one oxygen atom form stable complexes with alkali earth metal cations. This phenomenon can be explained on the grounds of the well known theory of hard and soft acids and bases. Uracil and thymine make complexes only when in their deprotonoted forms. The cations of great radii (Sr(2+), Ba(2+)) are more prone to form complexes of stoichiometry 1:1 with uracil and thymine than the cations of small radii (Mg(2+), Ca(2+)). On the other hand, Mg(2+) forms complexes of stoichiometry 2:1 and 3:2 with uracil and thymine. Gas-phase stabilities of the 1:1 complexes are higher for the cations of small radii, in contrast to the solution stabilities. For cytosine and 9- methylhypoxantine the 1:1 complexes of their deprotonated forms are observed at higher cone voltage as a result of HCl molecule loss from the complexes containing the counter ion (Cl(-)). In solution, more stable complexes are formed with metal cations of low radii. Gas-phase stability of the complexes formed by deprotonated 9- methyl-hypoxantine increases with increasing metal cation radius.

Glycomics expression analysis of sulfated glycosaminoglycans of human colorectal cancer tissues and non-neoplastic mucosa by electrospray ionization mass spectrometry.

Science.gov (United States)

Marolla, Ana Paula Cleto; Waisberg, Jaques; Saba, Gabriela Tognini; Waisberg, Daniel Reis; Margeotto, Fernando Beani; Pinhal, Maria Aparecida da Silva

2015-01-01

To determine the presence of glycosaminoglycans in the extracellular matrix of connective tissue from neoplastic and non-neoplastic colorectal tissues, since it has a central role in tumor development and progression. Tissue samples from neoplastic and non-neoplastic colorectal tissues were obtained from 64 operated patients who had colorectal carcinoma with no distant metastases. Expressions of heparan sulphate, chondroitin sulphate, dermatan sulphate and their fragments were analyzed by electrospray ionization mass spectrometry, with the technique for extraction and quantification of glycosaminoglycans after proteolysis and electrophoresis. The statistical analysis included mean, standard deviation, and Student'st test. The glycosaminoglycans extracted from colorectal tissue showed three electrophoretic bands in agarose gel. Electrospray ionization mass spectrometry showed characteristic disaccharide fragments from glycosaminoglycans, indicating their structural characterization in the tissues analyzed. Some peaks in the electrospray ionization mass spectrometry were not characterized as fragments of sugars, indicating the presence of fragments of the protein structure of proteoglycans generated during the glycosaminoglycan purification. The average amount of chondroitin and dermatan increased in the neoplastic tissue compared to normal tissue (p=0.01). On the other hand, the average amount of heparan decreased in the neoplastic tissue compared to normal tissue (p= 0.03). The method allowed the determination of the glycosaminoglycans structural profile in colorectal tissue from neoplastic and non-neoplastic colorectal tissue. Neoplastic tissues showed greater amounts of chondroitin sulphate and dermatan sulphate compared to non-neoplastic tissues, while heparan sulphate was decreased in neoplastic tissues.

Glycomics expression analysis of sulfated glycosaminoglycans of human colorectal cancer tissues and non-neoplastic mucosa by electrospray ionization mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Marolla, Ana Paula Cleto [Universidade Federal de São Paulo, São Paulo, SP (Brazil); Waisberg, Jaques [Hospital do Servidor Público Estadual, São Paulo, SP (Brazil); Faculdade de Medicina do ABC, Santo André, SP (Brazil); Saba, Gabriela Tognini [Faculdade de Medicina do ABC, Santo André, SP (Brazil); Waisberg, Daniel Reis [Faculdade de Medicina da Universidade de São Paulo, São Paulo, SP (Brazil); Margeotto, Fernando Beani; Pinhal, Maria Aparecida da Silva [Faculdade de Medicina do ABC, Santo André, SP (Brazil)

2015-07-01

To determine the presence of glycosaminoglycans in the extracellular matrix of connective tissue from neoplastic and non-neoplastic colorectal tissues, since it has a central role in tumor development and progression. Tissue samples from neoplastic and non-neoplastic colorectal tissues were obtained from 64 operated patients who had colorectal carcinoma with no distant metastases. Expressions of heparan sulphate, chondroitin sulphate, dermatan sulphate and their fragments were analyzed by electrospray ionization mass spectrometry, with the technique for extraction and quantification of glycosaminoglycans after proteolysis and electrophoresis. The statistical analysis included mean, standard deviation, and Student’s t test. The glycosaminoglycans extracted from colorectal tissue showed three electrophoretic bands in agarose gel. Electrospray ionization mass spectrometry showed characteristic disaccharide fragments from glycosaminoglycans, indicating their structural characterization in the tissues analyzed. Some peaks in the electrospray ionization mass spectrometry were not characterized as fragments of sugars, indicating the presence of fragments of the protein structure of proteoglycans generated during the glycosaminoglycan purification. The average amount of chondroitin and dermatan increased in the neoplastic tissue compared to normal tissue (p=0.01). On the other hand, the average amount of heparan decreased in the neoplastic tissue compared to normal tissue (p= 0.03). The method allowed the determination of the glycosaminoglycans structural profile in colorectal tissue from neoplastic and non-neoplastic colorectal tissue. Neoplastic tissues showed greater amounts of chondroitin sulphate and dermatan sulphate compared to non-neoplastic tissues, while heparan sulphate was decreased in neoplastic tissues.

Glycomics expression analysis of sulfated glycosaminoglycans of human colorectal cancer tissues and non-neoplastic mucosa by electrospray ionization mass spectrometry

International Nuclear Information System (INIS)

Marolla, Ana Paula Cleto; Waisberg, Jaques; Saba, Gabriela Tognini; Waisberg, Daniel Reis; Margeotto, Fernando Beani; Pinhal, Maria Aparecida da Silva

2015-01-01

To determine the presence of glycosaminoglycans in the extracellular matrix of connective tissue from neoplastic and non-neoplastic colorectal tissues, since it has a central role in tumor development and progression. Tissue samples from neoplastic and non-neoplastic colorectal tissues were obtained from 64 operated patients who had colorectal carcinoma with no distant metastases. Expressions of heparan sulphate, chondroitin sulphate, dermatan sulphate and their fragments were analyzed by electrospray ionization mass spectrometry, with the technique for extraction and quantification of glycosaminoglycans after proteolysis and electrophoresis. The statistical analysis included mean, standard deviation, and Student’s t test. The glycosaminoglycans extracted from colorectal tissue showed three electrophoretic bands in agarose gel. Electrospray ionization mass spectrometry showed characteristic disaccharide fragments from glycosaminoglycans, indicating their structural characterization in the tissues analyzed. Some peaks in the electrospray ionization mass spectrometry were not characterized as fragments of sugars, indicating the presence of fragments of the protein structure of proteoglycans generated during the glycosaminoglycan purification. The average amount of chondroitin and dermatan increased in the neoplastic tissue compared to normal tissue (p=0.01). On the other hand, the average amount of heparan decreased in the neoplastic tissue compared to normal tissue (p= 0.03). The method allowed the determination of the glycosaminoglycans structural profile in colorectal tissue from neoplastic and non-neoplastic colorectal tissue. Neoplastic tissues showed greater amounts of chondroitin sulphate and dermatan sulphate compared to non-neoplastic tissues, while heparan sulphate was decreased in neoplastic tissues

Recent advancements in sputter-type heavy negative ion sources

International Nuclear Information System (INIS)

Alton, G.D.

1989-01-01

Significant advancement have been made in sputter-type negative ion sources which utilize direct surface ionization, or a plasma to form the positive ion beam used to effect sputtering of samples containing the material of interest. Typically, such sources can be used to generate usable beam intensities of a few μA to several mA from all chemically active elements, depending on the particular source and the electron affinity of the element in question. The presentation will include an introduction to the fundamental processes underlying negative ion formation by sputtering from a low work function surface and several sources will be described which reflect the progress made in this technology. 21 refs., 9 figs., 1 tab

High-current negative hydrogen ion beam production in a cesium-injected multicusp source

International Nuclear Information System (INIS)

Takeiri, Y.; Tsumori, K.; Kaneko, O.

1997-01-01

A high-current negative hydrogen ion source has been developed, where 16.2 A of the H - current was obtained with a current density of 31 mA/cm 2 . The ion source is a multicusp source with a magnetic filter for negative ion production, and cesium vapor is injected into the arc chamber, leading to enhancement of the negative ion yields. The cesium-injection effects are discussed, based on the experimental observations. Although the surface production of the negative ions on the cesium-covered plasma grid is thought to be a dominant mechanism of the H - current enhancement, the cesium effects in the plasma volume, such as the cesium ionization and the electron cooling, are observed, and could contribute to the improved operation of the negative ion source. (author)

Laser-ablation electrospray ionization mass spectrometry with ion mobility separation reveals metabolites in the symbiotic interactions of soybean roots and rhizobia

Energy Technology Data Exchange (ETDEWEB)

Stopka, Sylwia A.; Agtuca, Beverly J.; Koppenaal, David W.; Pasa Tolic, Ljiljana; Stacey, Gary; Vertes, Akos; Anderton, Christopher R.

2017-05-23

Technologies enabling in situ metabolic profiling of living plant systems are invaluable for understanding physiological processes and could be used for rapid phenotypic screening (e.g., to produce plants with superior biological nitrogen fixing ability). The symbiotic interaction between legumes and nitrogen-fixing soil bacteria results in a specialized plant organ (i.e., root nodule), where the exchange of nutrients between host and endosymbiont occurs. Laser ablation electrospray ionization mass spectrometry (LAESI-MS) is a method that can be performed under ambient conditions requiring minimal sample preparation. Here, we employed LAESI-MS to explore the well-characterized symbiosis between soybean (Glycine max L. Merr.) and its compatible symbiont, Bradyrhizobium japonicum. The utilization of ion mobility separation (IMS) improved the molecular coverage, selectivity, and identification of the detected biomolecules. Specifically, incorporation of IMS resulted in an increase of 153 detected metabolites in the nodule samples. The data presented demonstrates the advantages of using LAESI-IMS-MS for the rapid analysis of intact root nodules, uninfected root segments, and free-living rhizobia. Untargeted pathway analysis revealed several metabolic processes within the nodule (e.g., zeatin, riboflavin, and purine synthesis). Compounds specific to the uninfected root and bacteria were also detected. Lastly, we performed depth-profiling of intact nodules to reveal the location of metabolites to the cortex and inside the infected region, and lateral profiling of sectioned nodules confirmed these molecular distributions. Our results established the feasibility of LAESI-IMS-MS for the analysis and spatial mapping of plant tissues, with its specific demonstration to improve our understanding of the soybean-rhizobial symbiosis.

A Multi-Sample Cs-Sputter Negative Ion Source

International Nuclear Information System (INIS)

Alton, G.D.; Ball, J.A.; Bao, Y.; Cui, B.; Reed, C.A.; Williams, C.

1998-01-01

A multi-sample Cs sputter negative-ion source, equipped with a conical-geometry, W-surface-ionizer has been designed and fabricated that permits sample changes without disruption of on-line accelerator operation. Sample changing is effected by actuating an electro-pneumatic control system located at ground potential that drives an air-motor-driven sample-indexing-system mounted at high voltage; this arrangement avoids complications associated with indexing mechanisms that rely on electronic power-supplies located at high potential. In-beam targets are identified by LED indicator lights derived from a fiber-optic, Gray-code target-position sensor. Aspects of the overall source design and details of the indexing mechanism along with operational parameters, ion optics. intensities, and typical emittances for a variety of negative-ion species will be presented in this report

A Multi-Sample Cs-Sputter Negative Ion Source

Energy Technology Data Exchange (ETDEWEB)

Alton, G.D.; Ball, J.A.; Bao, Y.; Cui, B.; Reed, C.A.; Williams, C.

1998-10-05

A multi-sample Cs sputter negative-ion source, equipped with a conical-geometry, W-surface-ionizer has been designed and fabricated that permits sample changes without disruption of on-line accelerator operation. Sample changing is effected by actuating an electro-pneumatic control system located at ground potential that drives an air-motor-driven sample-indexing-system mounted at high voltage; this arrangement avoids complications associated with indexing mechanisms that rely on electronic power-supplies located at high potential. In-beam targets are identified by LED indicator lights derived from a fiber-optic, Gray-code target-position sensor. Aspects of the overall source design and details of the indexing mechanism along with operational parameters, ion optics. intensities, and typical emittances for a variety of negative-ion species will be presented in this report.

Ionization efficiency calculations for cavity thermoionization ion source

International Nuclear Information System (INIS)

Turek, M.; Pyszniak, K.; Drozdziel, A.; Sielanko, J.; Maczka, D.; Yuskevich, Yu.V.; Vaganov, Yu.A.

2009-01-01

The numerical model of ionization in a thermoionization ion source is presented. The review of ion source ionization efficiency calculation results for various kinds of extraction field is given. The dependence of ionization efficiency on working parameters like ionizer length and extraction voltage is discussed. Numerical simulations results are compared to theoretical predictions obtained from a simplified ionization model

Vacancies and negative ions in GaAs

International Nuclear Information System (INIS)

Corbel, C.

1991-01-01

We use positron lifetime studies performed in GaAs materials to show the defect properties which can be investigated by implanting positive positrons in semiconductors. The studies concern native and electron irradiation induced defects. These studies show that vacancy charge state and vacancy ionization levels can be determined from positron annihilation. They show also that positrons are trapped by negative ions and give information on their concentration

Study of surface ionization and LASER ionization processes using the SOMEIL ion source: application to the Spiral 2 laser ion source development

Energy Technology Data Exchange (ETDEWEB)

Bajeat, O., E-mail: bajeat@ganil.fr; Lecesne, N.; Leroy, R.; Maunoury, L.; Osmond, B.; Sjodin, M. [GANIL (France); Maitre, A.; Pradeilles, N. [Laboratoire Science des Procedes Ceramiques et de Traitements de Surface (SPCTS) 12 (France)

2013-04-15

SPIRAL2 is the new project under construction at GANIL to provide radioactive ion beams to the Nuclear Physics Community and in particular neutron rich ion beams. For the production of condensable radioactive elements, a resonant ionization laser ion source is under development at GANIL. In order to generate the ions of interest with a good selectivity and purity, our group is studying the way to minimize surface ionization process by using refractory materials with low work function as ionizer tube. To do those investigations a dedicated ion source, called SOMEIL (Source Optimisee pour les Mesures d'Efficacite d'Ionisation Laser) is used. Numerous types of ionizer tubes made in various materials and geometry are tested. Surface ionization and laser ionization efficiencies can be measured for each of them.

Many-electron phenomena in the ionization of ions

International Nuclear Information System (INIS)

Mueller, A.

2004-01-01

Full text: Single and multiple ionization in ion-atom collisions involve a multitude of complex interactions between the electrons and nuclei of projectile and target. Some of the complexity is avoided in studies of fast collisions when the impulse approximation can be applied and the electrons can be described as independent quasi-free particles with a known momentum distribution. For the detailed investigation of ionization mechanisms that can occur in fast ion-atom collisions, it is illuminating to consider collisions of ions (or atoms) and really free electrons with a narrow energy spread. High energy resolution in electron-ion collision studies provides access to individual, possibly even state-selective, reaction pathways. Even in the simple electron-ion collision system (simple compared with the initial ion-atom problem) single and multiple ionization still involve a multitude of complex mechanisms. Besides the direct removal of one or several electrons from the target by electron impact, resonant and non-resonant formation of intermediate multiply excited states which subsequently decay by electron emission is important in single and multiple ionization of ions and atoms. Direct ionization proceeds via one-step or multi-step knock-off mechanisms which can partly be disentangled by studying effects of different projectile species. The role of multiply excited states in the ionization can be experimentally studied in great detail by a further reduction of the initial ion-atom problem. Multiply excited states of atoms and ions can be selectively populated by photon-ion interactions making use of the potential for extreme energy resolution made available at modern synchrotron radiation sources. In the review talk, examples of studies on single and multiple ionization in electron-ion collisions will be discussed in some detail. Electron-ion collision experiments will also be compared with photon-ion interaction studies. Many-electron phenomena have been observed

Development of a method for comprehensive and quantitative analysis of plant hormones by highly sensitive nanoflow liquid chromatography-electrospray ionization-ion trap mass spectrometry

International Nuclear Information System (INIS)

Izumi, Yoshihiro; Okazawa, Atsushi; Bamba, Takeshi; Kobayashi, Akio; Fukusaki, Eiichiro

2009-01-01

In recent plant hormone research, there is an increased demand for a highly sensitive and comprehensive analytical approach to elucidate the hormonal signaling networks, functions, and dynamics. We have demonstrated the high sensitivity of a comprehensive and quantitative analytical method developed with nanoflow liquid chromatography-electrospray ionization-ion trap mass spectrometry (LC-ESI-IT-MS/MS) under multiple-reaction monitoring (MRM) in plant hormone profiling. Unlabeled and deuterium-labeled isotopomers of four classes of plant hormones and their derivatives, auxins, cytokinins (CK), abscisic acid (ABA), and gibberellins (GA), were analyzed by this method. The optimized nanoflow-LC-ESI-IT-MS/MS method showed ca. 5-10-fold greater sensitivity than capillary-LC-ESI-IT-MS/MS, and the detection limits (S/N = 3) of several plant hormones were in the sub-fmol range. The results showed excellent linearity (R 2 values of 0.9937-1.0000) and reproducibility of elution times (relative standard deviations, RSDs, <1.1%) and peak areas (RSDs, <10.7%) for all target compounds. Further, sample purification using Oasis HLB and Oasis MCX cartridges significantly decreased the ion-suppressing effects of biological matrix as compared to the purification using only Oasis HLB cartridge. The optimized nanoflow-LC-ESI-IT-MS/MS method was successfully used to analyze endogenous plant hormones in Arabidopsis and tobacco samples. The samples used in this analysis were extracted from only 17 tobacco dry seeds (1 mg DW), indicating that the efficiency of analysis of endogenous plant hormones strongly depends on the detection sensitivity of the method. Our analytical approach will be useful for in-depth studies on complex plant hormonal metabolism.

Development of a method for comprehensive and quantitative analysis of plant hormones by highly sensitive nanoflow liquid chromatography-electrospray ionization-ion trap mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Izumi, Yoshihiro; Okazawa, Atsushi; Bamba, Takeshi; Kobayashi, Akio [Department of Biotechnology, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan); Fukusaki, Eiichiro, E-mail: fukusaki@bio.eng.osaka-u.ac.jp [Department of Biotechnology, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan)

2009-08-26

In recent plant hormone research, there is an increased demand for a highly sensitive and comprehensive analytical approach to elucidate the hormonal signaling networks, functions, and dynamics. We have demonstrated the high sensitivity of a comprehensive and quantitative analytical method developed with nanoflow liquid chromatography-electrospray ionization-ion trap mass spectrometry (LC-ESI-IT-MS/MS) under multiple-reaction monitoring (MRM) in plant hormone profiling. Unlabeled and deuterium-labeled isotopomers of four classes of plant hormones and their derivatives, auxins, cytokinins (CK), abscisic acid (ABA), and gibberellins (GA), were analyzed by this method. The optimized nanoflow-LC-ESI-IT-MS/MS method showed ca. 5-10-fold greater sensitivity than capillary-LC-ESI-IT-MS/MS, and the detection limits (S/N = 3) of several plant hormones were in the sub-fmol range. The results showed excellent linearity (R{sup 2} values of 0.9937-1.0000) and reproducibility of elution times (relative standard deviations, RSDs, <1.1%) and peak areas (RSDs, <10.7%) for all target compounds. Further, sample purification using Oasis HLB and Oasis MCX cartridges significantly decreased the ion-suppressing effects of biological matrix as compared to the purification using only Oasis HLB cartridge. The optimized nanoflow-LC-ESI-IT-MS/MS method was successfully used to analyze endogenous plant hormones in Arabidopsis and tobacco samples. The samples used in this analysis were extracted from only 17 tobacco dry seeds (1 mg DW), indicating that the efficiency of analysis of endogenous plant hormones strongly depends on the detection sensitivity of the method. Our analytical approach will be useful for in-depth studies on complex plant hormonal metabolism.

Simultaneous imaging of multiple neurotransmitters and neuroactive substances in the brain by desorption electrospray ionization mass spectrometry

OpenAIRE

Shariatgorji, Mohammadreza; Strittmatter, Nicole; Nilsson, Anna; Kallbäck, Patrik; Alvarsson, Alexandra; Zhang, Xiaoqun; Vallianatou, Theodosia; Svenningsson, Per; Goodwin, Richard J. A.; Andrén, Per E.

2016-01-01

With neurological processes involving multiple neurotransmitters and neuromodulators, it is important to have the ability to directly map and quantify multiple signaling molecules simultaneously in a single analysis. By utilizing a molecular-specific approach, namely desorption electrospray ionization mass spectrometry imaging (DESI-MSI), we demonstrated that the technique can be used to image multiple neurotransmitters and their metabolites (dopamine, dihydroxyphenylacetic acid, 3-methoxytyr...

Detection of Metastatic Breast and Thyroid Cancer in Lymph Nodes by Desorption Electrospray Ionization Mass Spectrometry Imaging

Science.gov (United States)

Zhang, Jialing; Feider, Clara L.; Nagi, Chandandeep; Yu, Wendong; Carter, Stacey A.; Suliburk, James; Cao, Hop S. Tran; Eberlin, Livia S.

2017-06-01

Ambient ionization mass spectrometry has been widely applied to image lipids and metabolites in primary cancer tissues with the purpose of detecting and understanding metabolic changes associated with cancer development and progression. Here, we report the use of desorption electrospray ionization mass spectrometry (DESI-MS) to image metastatic breast and thyroid cancer in human lymph node tissues. Our results show clear alterations in lipid and metabolite distributions detected in the mass spectra profiles from 42 samples of metastatic thyroid tumors, metastatic breast tumors, and normal lymph node tissues. 2D DESI-MS ion images of selected molecular species allowed discrimination and visualization of specific histologic features within tissue sections, including regions of metastatic cancer, adjacent normal lymph node, and fibrosis or adipose tissues, which strongly correlated with pathologic findings. In thyroid cancer metastasis, increased relative abundances of ceramides and glycerophosphoinisitols were observed. In breast cancer metastasis, increased relative abundances of various fatty acids and specific glycerophospholipids were seen. Trends in the alterations in fatty acyl chain composition of lipid species were also observed through detailed mass spectra evaluation and chemical identification of molecular species. The results obtained demonstrate DESI-MSI as a potential clinical tool for the detection of breast and thyroid cancer metastasis in lymph nodes, although further validation is needed. [Figure not available: see fulltext.

Coordination chemistry of nickel(II) nitrate with superbasic guanidines studied by electrospray mass spectrometry

Czech Academy of Sciences Publication Activity Database

Glasovac, Z.; Štrukil, V.; Eckert-Maksič, M.; Schröder, Detlef; Schlangen, M.; Schwarz, H.

2010-01-01

Roč. 290, č. 1 (2010), s. 22-31 ISSN 1387-3806 R&D Projects: GA ČR GA203/08/1487 Grant - others: ERC (XE) HORIZOMS AdG226373 Institutional research plan: CEZ:AV0Z40550506 Keywords : electrospray ionization * guanidine * ion association * nickel(II) nitrate * solvation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.009, year: 2010

Multiple ionization of atoms by ion impact

International Nuclear Information System (INIS)

DuBois, R.D.

1988-01-01

In order to model the energy deposition of fast ions as they slow down in gaseous media, information about the ionization occurring in collisions between ions and target atoms/molecules is required. Our measurements of doubly differential electron emission cross sections provide detailed information about the ionization process but do not provide any information about the final states of the target. They also do not distinguish between the emission of one or more target electrons in a single collision. It is important to know the relative importance of multiple-, with respect to single-, target ionization in order to accurately model the energy deposition. To date, multiple ionization of He, Ne, Ar, Kr, and Xe targets has been studied. Primarily, H and He ions were used, although some data for heavier ions (C,N and O) have also been obtained

Selective and sensitive detection of chromium(VI) in waters using electrospray ionization mass spectrometry.

Science.gov (United States)

Weldy, Effie; Wolff, Chloe; Miao, Zhixin; Chen, Hao

2013-09-01

From 2000 through 2011, there were 14 criminal cases of violations of the Clean Water Act involving the discharge of chromium, a toxic heavy metal, into drinking and surface water sources. As chromium(VI), a potential carcinogen present in the environment, represents a significant safety concern, it is currently the subject of an EPA health risk assessment. Therefore, sensitive and selective detection of this species is highly desired. This study reports the analysis of chromium(VI) in water samples by electrospray ionization mass spectrometry (ESI-MS) following its reduction and complexation with ammonium pyrrolidinedithiocarbamate (APDC). The reduction and subsequent complexation produce a characteristic [Cr(III)O]-PDC complex which can be detected as a protonated ion of m/z 507 in the positive ion mode. The detection is selective to chromium(VI) under acidic pH, even in the presence of chromium(III) and other metal ions, providing high specificity. Different water samples were examined, including deionized, tap, and river waters, and sensitive detection was achieved. In the case of deionized water, quantification over the concentration range of 3.7 to 148ppb gave an excellent correlation coefficient of 0.9904 using the enhanced MS mode scan. Using the single-reaction monitoring (SRM) mode (monitoring the characteristic fragmentation of m/z 507 to m/z 360), the limit of detection (LOD) was found to be 0.25ppb. The LOD of chromium(VI) for both tap and river water samples was determined to be 2.0ppb. A preconcentration strategy using simple vacuum evaporation of the aqueous sample was shown to further improve the ESI signal by 15 fold. This method, with high sensitivity and selectivity, should provide a timely solution for the real-world analysis of toxic chromium(VI). Copyright © 2012 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

Electro-spray Ionization Mass Spectrometry Investigation of BTBP - Lanthanide(III) and Actinide(III) Complexes

Energy Technology Data Exchange (ETDEWEB)

Retegan, T.; Ekberg, Ch. [Chalmers, Dept Chem and Biol Engn, SE-41296 Gothenburg, (Sweden); Berthon, L.; Zorz, N. [DEN DRCP SCPS LCSE, CEA Marcoule, Bagnols Sur Ceze, (France)

2009-07-01

In the framework of nuclear waste reprocessing, the separation processes of minor actinides from fission products are developed using liquid-liquid extraction. To gain an understanding of the mechanism involved in the extraction process, a complex formation of actinides and lanthanides with BTBPs (6, 6'-bis(5, 6-dialkyl-1, 2, 4-triazin-3-yl)-2, 2'-bipyridines) was characterized using the Electro-spray Ionization Mass Spectrometry (ESI-MS) technique. This study was carried out to compare the influence of diluents and side groups of the extractants on complex formation. Three different diluents, nitrobenzene, octanol and cyclohexanone, and two extractants, C5-BTBP and CyMe{sub 4}-BTBP, were selected for this experiment. It was found that the change of the diluent and of the substituent on the BTBP moiety does not modify the stoichiometry of the complexes which is L{sub 2}M(NO{sub 3}){sub 3}. It is proposed that one nitrate is directly coordinated to the metal ion, the two other anions probably remaining in the outer coordination sphere. The difference observed in extracting properties is probably due to the solvation of the complexes by the diluent. The noncovalent force that holds complexes together are likely to be largely governed by electrostatic interactions even if the hydrophobic exterior of the complexes plays an important role in the complexation/extraction mechanism. The study of the stability of the ions in the gas phase shows that the C5-BTBP ligand has a labile hydrogen atom, which is a fragility point of C5-BTBP. (authors)

Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Science.gov (United States)

Koch, Boris P.; Witt, Matthias; Engbrodt, Ralph; Dittmar, Thorsten; Kattner, Gerhard

2005-07-01

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.

Improving the selectivity and sensitivity for quantifying 8-α-hydroxy-mutilin in rabbit tissues by using basic mobile phases and negative ionization.

Science.gov (United States)

Tan, Aimin; Gu, Guifen; Gui, Xuan; Wu, Yanxin; Bolger, Gordon; Licollari, Albert; Fanaras, John C

2018-01-01

Previously reported LC-MS methods for quantifying 8-α-hydroxy-mutilin (a marker residue of tiamulin) in tissues all used a pseudo MRM transition (from protonated molecular ion to protonated molecular ion, m/z 337→337) due to difficulties in finding a product ion, leading to suboptimal selectivity and sensitivity for detection. By using electrospray negative ionization in a basic medium, we, for the first time, found a highly selective and sensitive true MRM transition for 8-α-hydroxy-mutilin, m/z 335→179. With this newly found MRM transition and the use of pleuromutilin as the internal standard, a very sensitive, selective, and robust LC-MS/MS method has been developed and validated for quantifying 8-α-hydroxy-mutilin in rabbit tissues (muscle, liver, kidney, and fat). In comparison with the previously published methods, the selectivity and sensitivity were significantly improved. For the concentration range validated (0.2-10ppm or 0.2-10μg/g), the within-run and between-run accuracies (% bias) ranged from -5.0 to 3.1 and -4.9 to 3.0, respectively. The% CV ranged from 2.2 to 6.6 and 4.7 to 8.3 for within-run and between-run precisions, respectively. The validated method was successfully used to support two GLP tissue residue depletion studies in rabbits. Copyright © 2017 Elsevier B.V. All rights reserved.

Simultaneous determination of water-soluble vitamins in selected food matrices by liquid chromatography/electrospray ionization tandem mass spectrometry.

Science.gov (United States)

Gentili, Alessandra; Caretti, Fulvia; D'Ascenzo, Giuseppe; Marchese, Stefano; Perret, Daniela; Di Corcia, Daniele; Rocca, Lucia Mainero

2008-07-01

A rapid, simple and sensitive method based on liquid chromatography/tandem mass spectrometry (LC/MS/MS) with an electrospray ionization (ESI) source for the simultaneous analysis of fourteen water-soluble vitamins (B1, B2, two B3 vitamers, B5, five B6 vitamers, B8, B9, B12 and C) in various food matrices, i.e. maize flour, green and golden kiwi and tomato pulp, is presented here. Analytes were separated by ion-suppression reversed-phase liquid chromatography in less than 10 min and detected in positive ion mode. Sensitivity and specificity of this method allowed two important results to be achieved: (i) limits of detection of the analytes at ng g(-1) levels (except for vitamin C); (ii) development of a rapid sample treatment that minimizes analyte exposition to light, air and heat, eliminating any step of extract concentration. Analyte recovery depended on the type of matrix. In particular, recovery of the analytes in maize flour was > or =70%, with the exception of vitamin C, pyridoxal-5'-phosphate and vitamin B9 (ca 40%); with tomato pulp, recovery was > or =64%, except for vitamin C (41%); with kiwi, recovery was > or =73%, except for nicotinamide (ca. 30%).

Aerosol Vacuum-Assisted Plasma Ionization (Aero-VaPI) Coupled to Ion Mobility-Mass Spectrometry

Science.gov (United States)

Blair, Sandra L.; Ng, Nga L.; Zambrzycki, Stephen C.; Li, Anyin; Fernández, Facundo M.

2018-02-01

In this communication, we report on the real-time analysis of organic aerosol particles by Vacuum-assisted Plasma Ionization-Mass Spectrometry (Aero-VaPI-MS) using a home-built VaPI ion source coupled to a Synapt G2-S HDMS ion mobility-mass spectrometry (IM-MS) system. Standards of organic molecules of interest in prebiotic chemistry were used to generate aerosols. Monocaprin and decanoic acid aerosol particles were successfully detected in both the positive and negative ion modes, respectively. A complex aerosol mixture of different sizes of polymers of L-malic acid was also examined through ion mobility (IM) separations, resulting in the detection of polymers of up to eight monomeric units. This noncommercial plasma ion source is proposed as a low cost alternative to other plasma ionization platforms used for aerosol analysis, and a higher-performance alternative to more traditional aerosol mass spectrometers. VaPI provides robust online ionization of organics in aerosols without extensive ion activation, with the coupling to IM-MS providing higher peak capacity and excellent mass accuracy. [Figure not available: see fulltext.

Redox reactions of copper(II) upon electrospray ionization in the presence of acridine ligands with an amide side chain

Czech Academy of Sciences Publication Activity Database

Tintaru, A.; Charles, L.; Milko, Petr; Roithová, J.; Schröder, Detlef

2009-01-01

Roč. 22, č. 3 (2009), s. 229-233 ISSN 0894-3230 R&D Projects: GA AV ČR KJB400550704; GA ČR GA203/08/1487 Institutional research plan: CEZ:AV0Z40550506 Keywords : acridine * copper * electrospray ionization * mass spectrometry * quinoline Subject RIV: CC - Organic Chemistry Impact factor: 1.602, year: 2009

Development of a multiplexed interface for capillary electrophoresis-electrospray ion trap mass spectrometry.

Science.gov (United States)

Li, Fu-An; Wu, Ming-Chi; Her, Guor-Rong

2006-08-01

A four-channel multiplexed electrospray capillary electrophoresis interface has been developed. This new interface permits up to four capillary electrophoresis columns to be sampled sequentially by means of a stepper motor and a notched rotating plate assembly, which at any instant occludes all but a single sprayer. In this design, four sheath liquid electrospray probes are oriented in a circular array situated 90 degrees relative to one another. The rotating metal disk, which contains a one-quarter notch, is mounted to the stepper motor assembly and is located between the sprayers and the entrance aperture of an ion trap mass spectrometer. By using the data acquisition signal from the ion trap mass spectrometer, the scan event is synchronized with the rotation of the metal disk. With this device, four discrete sample streams can be simultaneously analyzed, resulting in a 4-fold increase in analytical throughput.

Rapid Quantification of Low-Viscosity Acetyl-Triacylglycerols Using Electrospray Ionization Mass Spectrometry.

Science.gov (United States)

Bansal, Sunil; Durrett, Timothy P

2016-09-01

Acetyl-triacylglycerols (acetyl-TAG) possess an sn-3 acetate group, which confers useful chemical and physical properties to these unusual triacylglycerols (TAG). Current methods for quantification of acetyl-TAG are time consuming and do not provide any information on the molecular species profile. Electrospray ionization mass spectrometry (ESI-MS)-based methods can overcome these drawbacks. However, the ESI-MS signal intensity for TAG depends on the aliphatic chain length and unsaturation index of the molecule. Therefore response factors for different molecular species need to be determined before any quantification. The effects of the chain length and the number of double-bonds of the sn-1/2 acyl groups on the signal intensity for the neutral loss of short chain length sn-3 groups were quantified using a series of synthesized sn-3 specific structured TAG. The signal intensity for the neutral loss of the sn-3 acyl group was found to negatively correlated with the aliphatic chain length and unsaturation index of the sn-1/2 acyl groups. The signal intensity of the neutral loss of the sn-3 acyl group was also negatively correlated with the size of that chain. Further, the position of the group undergoing neutral loss was also important, with the signal from an sn-2 acyl group much lower than that from one located at sn-3. Response factors obtained from these analyses were used to develop a method for the absolute quantification of acetyl-TAG. The increased sensitivity of this ESI-MS-based approach allowed successful quantification of acetyl-TAG in various biological settings, including the products of in vitro enzyme activity assays.

Negative-ion-beam generation with the ORNL SITEX source

International Nuclear Information System (INIS)

Dagenhart, W.K.; Stirling, W.L.; Kim, J.

1982-05-01

Parametric studies were made on a hot cathode reflex discharge H - Surface Ionization source with Transverse Extraction (SITEX) in both the pure hydrogen and the mixed hydrogen-cesium mode. Extraction current density, beam current, gas efficiency, extracted electron-to-H - current ratio, heavy negative ion impurities, optics, and long pulse operation were investigated as a function of time, arc voltage, arc current, converter voltage, H 2 gas flow, cesium feed rate, and plasma generator geometries. Initial results of the research were an extracted H - beam current density of 56 mA/cm 2 at 23 mA for 5 s pulses and, gas efficiency of 3%, theta/sub perpendicular/ (1/e) approx. 2 +- 1 0 , theta/sub parallel/ (1/e) approx. 1 +- 1 0 , at a beam energy of 25 keV. Negative heavy ion beam impurities were reduced to - ions are produced prinicpally by positive ion surface conversion using elemental cesium fractional monolayer coverage on a molybdenum converter substrate, which is biased negatively with respect to the anode

Quantitative Caffeine Analysis Using a Surface Sampling Probe Electrospray Ionization Tandem Mass Spectrometry System

Energy Technology Data Exchange (ETDEWEB)

Ford, Michael J [ORNL; Deibel, Michael A. [Earlham College; Tomkins, Bruce A [ORNL; Van Berkel, Gary J [ORNL

2005-01-01

Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 {mu}m/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methods determined from the calibration curve statistics were 0.20 ng injected (0.50 {mu}L) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by 8% or more) than the literature values.

Negative Ion Density Fronts

International Nuclear Information System (INIS)

Igor Kaganovich

2000-01-01

Negative ions tend to stratify in electronegative plasmas with hot electrons (electron temperature Te much larger than ion temperature Ti, Te > Ti ). The boundary separating a plasma containing negative ions, and a plasma, without negative ions, is usually thin, so that the negative ion density falls rapidly to zero-forming a negative ion density front. We review theoretical, experimental and numerical results giving the spatio-temporal evolution of negative ion density fronts during plasma ignition, the steady state, and extinction (afterglow). During plasma ignition, negative ion fronts are the result of the break of smooth plasma density profiles during nonlinear convection. In a steady-state plasma, the fronts are boundary layers with steepening of ion density profiles due to nonlinear convection also. But during plasma extinction, the ion fronts are of a completely different nature. Negative ions diffuse freely in the plasma core (no convection), whereas the negative ion front propagates towards the chamber walls with a nearly constant velocity. The concept of fronts turns out to be very effective in analysis of plasma density profile evolution in strongly non-isothermal plasmas

Constant-Distance Mode Nanospray Desorption Electrospray Ionization Mass Spectrometry Imaging of Biological Samples with Complex Topography

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Son N.; Liyu, Andrey V.; Chu, Rosalie K.; Anderton, Christopher R.; Laskin, Julia

2017-01-17

A new approach for constant distance mode mass spectrometry imaging of biological samples using nanospray desorption electrospray ionization (nano-DESI MSI) was developed by integrating a shear-force probe with nano-DESI probe. The technical concept and basic instrumental setup as well as general operation of the system are described. Mechanical dampening of resonant oscillations due to the presence of shear forces between the probe and the sample surface enables constant-distance imaging mode via a computer controlled closed feedback loop. The capability of simultaneous chemical and topographic imaging of complex biological samples is demonstrated using living Bacillus Subtilis ATCC 49760 colonies on agar plates. The constant-distance mode nano-DESI MSI enabled imaging of many metabolites including non-ribosomal peptides (surfactin, plipastatin and iturin) and iron-bound heme on the surface of living bacterial colonies ranging in diameter from 10 mm to 13 mm with height variations of up to 0.8 mm above the agar plate. Co-registration of ion images to topographic images provided higher-contrast images. Constant-mode nano-DESI MSI is ideally suited for imaging biological samples of complex topography in their native state.

Occupancy of a C2-C2 type 'zinc-finger' protein domain by copper. Direct observation by electrospray ionization mass spectrometry.

Science.gov (United States)

Hutchens, T W; Allen, M H; Li, C M; Yip, T T

1992-09-07

The metal ion specificity of most 'zinc-finger' metal binding domains is unknown. The human estrogen receptor protein contains two different C2-C2 type 'zinc-finger' sequences within its DNA-binding domain (ERDBD). Copper inhibits the function of this protein by mechanisms which remain unclear. We have used electrospray ionization mass spectrometry to evaluate directly the 71-residue ERDBD (K180-M250) in the absence and presence of Cu(II) ions. The ERDBD showed a high affinity for Cu and was completely occupied with 4 Cu bound; each Cu ion was evidently bound to only two ligand residues (net loss of only 2 Da per bound Cu). The Cu binding stoichiometry was confirmed by atomic absorption. These results (i) provide the first direct physical evidence for the ability of the estrogen receptor DNA-binding domain to bind Cu and (ii) document a twofold difference in the Zn- and Cu-binding capacity. Differences in the ERDBD domain structure with bound Zn and Cu are predicted. Given the relative intracellular contents of Zn and Cu, our findings demonstrate the need to investigate further the Cu occupancy of this and other zinc-finger domains both in vitro and in vivo.

Study of ion suppression for phenolic compounds in medicinal plant extracts using liquid chromatography-electrospray tandem mass spectrometry.

Science.gov (United States)

Faccin, H; Viana, C; do Nascimento, P C; Bohrer, D; de Carvalho, L M

2016-01-04

A systematic study on the various sources of ion suppression in UHPLC-MS-MS analysis was carried out for 24 phenolic antioxidants in 6 different extracts of medicinal plants from Amazonia. The contributions of matrix effects, mobile-phase additives, analyte co-elution and electric charge competition during ionization to the global ion suppression were evaluated. Herein, the influence of mobile-phase additives on the ionization efficiency was found to be very pronounced, where ion suppression of approximately 90% and ion enhancement effects greater than 400% could be observed. The negative effect caused by the wrong choice of internal standard (IS) on quantitative studies was also evaluated and discussed from the perspective of ion suppression. This work also shows the importance of performing studies with this approach even for very similar matrices, such as varieties of medicinal plants from the same species, because different effects were observed for the same analyte. Copyright © 2015 Elsevier B.V. All rights reserved.

Experimental Evaluation of a Negative Ion Source for a Heavy Ion Fusion Negative Ion Driver

International Nuclear Information System (INIS)

Grisham, L.R.; Hahto, S.K.; Hahto, S.T.; Kwan, J.W.; Leung, K.N.

2004-01-01

Negative halogen ions have recently been proposed as a possible alternative to positive ions for heavy ion fusion drivers because electron accumulation would not be a problem in the accelerator, and if desired, the beams could be photo-detached to neutrals. To test the ability to make suitable quality beams, an experiment was conducted at Lawrence Berkeley National Laboratory using chlorine in an RF-driven ion source. Without introducing any cesium (which is required to enhance negative ion production in hydrogen ion sources) a negative chlorine current density of 45 mA/cm 2 was obtained under the same conditions that gave 57 45 mA/cm 2 of positive chlorine, suggesting the presence of nearly as many negative ions as positive ions in the plasma near the extraction plane. The negative ion spectrum was 99.5% atomic chlorine ions, with only 0.5% molecular chlorine, and essentially no impurities. Although this experiment did not incorporate the type of electron suppression technology that i s used in negative hydrogen beam extraction, the ratio of co-extracted electrons to Cl - was as low as 7 to 1, many times lower than the ratio of their mobilities, suggesting that few electrons are present in the near-extractor plasma. This, along with the near-equivalence of the positive and negative ion currents, suggests that the plasma in this region was mostly an ion-ion plasma. The negative chlorine current density was relatively insensitive to pressure, and scaled linearly with RF power. If this linear scaling continues to hold at higher RF powers, it should permit current densities of 100 45 mA/cm 2 , sufficient for present heavy ion fusion injector concepts. The effective ion temperatures of the positive and negative ions appeared to be similar and relatively low for a plasma source

Imaging of plant materials using indirect desorption electrospray ionization mass spectrometry

DEFF Research Database (Denmark)

Janfelt, Christian

2015-01-01

Indirect desorption electrospray ionization mass spectrometry (DESI-MS) imaging is a method for imaging distributions of metabolites in plant materials, in particular leaves and petals. The challenge in direct imaging of such plant materials with DESI-MS is particularly the protective layer of cu...... of interest from parts of their matrix while preserving the spatial information in the two dimensions. The imprint can then easily be imaged by DESI-MS. The method delivers simple and robust mass spectrometry imaging of plant material with very high success ratios....... of cuticular wax present in leaves and petals. The cuticle protects the plant from drying out, but also makes it difficult for the DESI sprayer to reach the analytes of interest inside the plant material. A solution to this problem is to imprint the plant material onto a surface, thus releasing the analytes...

Alkali suppression within laser ion-source cavities and time structure of the laser ionized ion-bunches

CERN Document Server

Lettry, Jacques; Köster, U; Georg, U; Jonsson, O; Marzari, S; Fedosseev, V

2003-01-01

The chemical selectivity of the target and ion-source production system is an asset for Radioactive Ion-Beam (RIB) facilities equipped with mass separators. Ionization via laser induced multiple resonant steps Ionization has such selectivity. However, the selectivity of the ISOLDE Resonant Ionization Laser Ion-Source (RILIS), where ionization takes place within high temperature refractory metal cavities, suffers from unwanted surface ionization of low ionization potential alkalis. In order to reduce this type of isobaric contaminant, surface ionization within the target vessel was used. On-line measurements of the efficiency of this method is reported, suppression factors of alkalis up to an order of magnitude were measured as a function of their ionization potential. The time distribution of the ion bunches produced with the RILIS was measured for a variety of elements and high temperature cavity materials. While all ions are produced within a few nanoseconds, the ion bunch sometimes spreads over more than 1...

Characterization of Nitrated Sugar Alcohols by Atmospheric-Pressure Chemical-Ionization Mass Spectrometry

Science.gov (United States)

2016-07-27

Chemical, Microsystem, and Nanoscale Technology Group MIT-Lincoln Laboratory, Lexington, MA 02420 jude.kelley@ll.mit.edu RATIONALE: The...formed by the loss of NO2, HNO2, NO3, and CH2NO2 groups , and in the presence of dichloromethane chlorinated adduct ions were observed. It was determined...explosives trace detection, such as electrospray ionization ( ESI ) and atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) along

Gas chromatography coupled to atmospheric pressure ionization mass spectrometry (GC-API-MS): review.

Science.gov (United States)

Li, Du-Xin; Gan, Lin; Bronja, Amela; Schmitz, Oliver J

2015-09-03

Although the coupling of GC/MS with atmospheric pressure ionization (API) has been reported in 1970s, the interest in coupling GC with atmospheric pressure ion source was expanded in the last decade. The demand of a "soft" ion source for preserving highly diagnostic molecular ion is desirable, as compared to the "hard" ionization technique such as electron ionization (EI) in traditional GC/MS, which fragments the molecule in an extensive way. These API sources include atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), atmospheric pressure laser ionization (APLI), electrospray ionization (ESI) and low temperature plasma (LTP). This review discusses the advantages and drawbacks of this analytical platform. After an introduction in atmospheric pressure ionization the review gives an overview about the history and explains the mechanisms of various atmospheric pressure ionization techniques used in combination with GC such as APCI, APPI, APLI, ESI and LTP. Also new developments made in ion source geometry, ion source miniaturization and multipurpose ion source constructions are discussed and a comparison between GC-FID, GC-EI-MS and GC-API-MS shows the advantages and drawbacks of these techniques. The review ends with an overview of applications realized with GC-API-MS. Copyright © 2015. Published by Elsevier B.V.

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

Science.gov (United States)

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. Copyright © 2014 Elsevier B.V. All rights reserved.

CFD SIMULATION OF AIR ION REGIME IN WORK AREAS AT CONDITION OF ARTIFICIAL AIR IONIZATION

Directory of Open Access Journals (Sweden)

M. M. Biliaiev

2016-02-01

Full Text Available Purpose. The paper supposes creation of a CFD model for calculating the air ion regime in the premises and in work areas at artificial ionization of the air by the ionizer installation indoors with considering the most important physical factors that influence the formation of ions concentration field. Methodology. The proposed CFD model for calculation of the air ion regime in work areas at artificial ionization of the air by installing ionizer indoors is based on the application of aerodynamics, electrostatics and mass transfer equations. The mass transfer equation takes into account the interaction of different polarities of ions with each other and with the dust particles. The calculation of air flow rate in the room is realized on the basis of the potential flow model by using the Laplace equation for the stream function. Poisson equation for the electric potential is used for calculation of the charged particles drift in an electric field. At the simulation to take into account: 1 influence of the working area geometric characteristics; 2 location of the ventilation holes; 3 placement of furniture and equipment; 4 ventilation regime in the room; 5 presence of obstacles on the ions dispersion process; 6 specific location of dust particles emission and ions of different polarity, and their interaction in the room and in the working zones. Findings. The developed CFD model allows determining the concentration of negative ions in the room and in the area of the human respiratory organs. The distribution of the negative ions concentration is presented in the form of concentration field isolines. Originality. The 2D CFD model for calculating the air ion regime in working areas, providing the ability to determine the ions concentration in a given place in the room was created. The proposed model is developed taking into account: placement of furniture and equipment in the room; geometric characteristics of the room; location of dust emissions

MoS_2/Ag nanohybrid: A novel matrix with synergistic effect for small molecule drugs analysis by negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

International Nuclear Information System (INIS)

Zhao, Yaju; Deng, Guoqing; Liu, Xiaohui; Sun, Liang; Li, Hui; Cheng, Quan; Xi, Kai; Xu, Danke

2016-01-01

This paper reports a facile synthesis of molybdenum disulfide nanosheets/silver nanoparticles (MoS_2/Ag) hybrid and its use as an effective matrix in negative ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The nanohybrid exerts a strong synergistic effect, leading to high performance detection of small molecule analytes including amino acids, peptides, fatty acids and drugs. The enhancement of laser desorption/ionization (LDI) efficiency is largely attributed to the high surface roughness and large surface area for analyte adsorption, better dispersibility, increased thermal conductivity and enhanced UV energy absorption as compared to pure MoS_2. Moreover, both Ag nanoparticles and the edge of the MoS_2 layers function as deprotonation sites for proton capture, facilitating the charging process in negative ion mode and promoting formation of negative ions. As a result, the MoS_2/Ag nanohybrid proves to be a highly attractive matrix in MALDI-TOF MS, with desired features such as high desorption/ionization efficiency, low fragmentation interference, high salt tolerance, and no sweet-spots for mass signal. These characteristic properties allowed for simultaneous analysis of eight different drugs and quantification of acetylsalicylic acid in the spiked human serum. This work demonstrates for the first time the fabrication and application of a novel MoS_2/Ag hybrid, and provides a new platform for use in the rapid and high throughput analysis of small molecules by mass spectrometry. - Highlights: • MoS_2/Ag nanohybrid was applied as a novel matrix in negative-ion MALDI-TOF MS. • The MoS_2/Ag nanohybrid exerted synergistic effect on the detection of small molecules. • The MoS_2/Ag nanohybrid showed good signal reproducibility and low background interferences comparing to organic matrices. • MoS_2/Ag allows simultaneous analysis of multiple drugs and quantification of acetylsalicylic acid in spiked serum samples.

Technical Note: Molecular characterization of aerosol-derived water soluble organic carbon using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Directory of Open Access Journals (Sweden)

R. M. Dickhut

2008-09-01

Full Text Available Despite the acknowledged relevance of aerosol-derived water-soluble organic carbon (WSOC to climate and biogeochemical cycling, characterization of aerosol WSOC has been limited. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS was utilized in this study to provide detailed molecular level characterization of the high molecular weight (HMW; m/z>223 component of aerosol-derived WSOC collected from rural sites in Virginia and New York, USA. More than 3000 peaks were detected by ESI FT-ICR MS within a m/z range of 223–600 for each sample. Approximately 86% (Virginia and 78% (New York of these peaks were assigned molecular formulas using only carbon (C, hydrogen (H, oxygen (O, nitrogen (N, and sulfur (S as elemental constituents. H/C and O/C molar ratios were plotted on van Krevelen diagrams and indicated a strong contribution of lignin-like and lipid-like compounds to the aerosol-derived WSOC samples. Approximately 1–4% of the peaks in the aerosol-derived WSOC mass spectra were classified as black carbon (BC on the basis of double bond equivalents calculated from the assigned molecular formulas. In addition, several high-magnitude peaks in the mass spectra of samples from both sites corresponded to molecular formulas proposed in previous secondary organic aerosol (SOA laboratory investigations indicating that SOAs are important constituents of the WSOC. Overall, ESI FT-ICR MS provides a level of resolution adequate for detailed compositional and source information of the HMW constituents of aerosol-derived WSOC.

Ionization of atoms by bare ion projectiles

International Nuclear Information System (INIS)

Tribedi, L.C.

1997-01-01

The double differential cross sections (DDCS) for low energy electron emission can provide stringent tests to the theoretical models for ionization in ion-atom collision. The two-center effects and the post collision interactions play a major role in ionization by highly charged, high Z projectiles. We close-quote ll review the recent developments in this field and describe our efforts to study the energy and angular distributions of the low energy electrons emitted in ion-atom ionization. copyright 1997 American Institute of Physics

Effect of cesium seeding on hydrogen negative ion volume production

International Nuclear Information System (INIS)

Bacal, M.; Balghiti-Sube, F. El; Elizarov, L. I.; Tontegode, A. J.

1998-01-01

The effect of cesium vapor partial pressure on the plasma parameters has been studied in the dc hybrid negative ion source ''CAMEMBERT III.'' The cesium vapor pressure was varied up to 10 -5 Torr and was determined by a surface ionization gauge in the absence of the discharge. The negative ion relative density measured by laser photodetachment in the center of the plasma extraction region increases by a factor of four when the plasma is seeded with cesium. However the plasma density and the electron temperature (determined using a cylindrical electrostatic probe) are reduced by the cesium seeding. As a result, the negative ion density goes up by a factor of two at the lowest hydrogen pressure studied. The velocity of the directed negative ion flow to the plasma electrode, determined from two-laser beam photodetachment experiments, appears to be affected by the cesium seeding. The variation of the extracted negative ion and electron currents versus the plasma electrode bias will also be reported for pure hydrogen and cesium seeded plasmas. The cesium seeding leads to a dramatic reduction of the electron component, which is consistent with the reduced electron density and temperature. The negative ion current is enhanced and a goes through a maximum at plasma electrode bias lower than 1 V. These observations lead to the conclusion that the enhancement of pure volume production occurs in this type of plasma. Possible mechanisms for this type of volume process will be discussed

Quantitative Determination of Bioactive Constituents in Noni Juice by High-performance Liquid Chromatography with Electrospray Ionization Triple Quadrupole Mass Spectrometry.

Science.gov (United States)

Yan, Yongqiu; Lu, Yu; Jiang, Shiping; Jiang, Yu; Tong, Yingpeng; Zuo, Limin; Yang, Jun; Gong, Feng; Zhang, Ling; Wang, Ping

2018-01-01

Noni juice has been extensively used as folk medicine for the treatment of arthritis, infections, analgesic, colds, cancers, and diabetes by Polynesians for many years. Due to the lack of standard scientific evaluation methods, various kinds of commercial Noni juice with different quality and price were available on the market. To establish a sensitive, reliable, and accurate high-performance liquid chromatography with electrospray ionization triple quadrupole mass spectrometry (HPLC-ESI-MS/MS) method for separation, identification, and simultaneous quantitative analysis of bioactive constituents in Noni juice. The analytes and eight batches of commercially available samples from different origins were separated and analyzed by the HPLC-ESI-MS/MS method on an Agilent ZORBAX SB-C 18 (150 mm × 4.6 mm i.d., 5 μm) column using a gradient elution of acetonitrile-methanol-0.05% glacial acetic acid in water (v/v) at a constant flow rate of 0.5 mL/min. Seven components were identification and all of the assay parameters were within the required limits. Components were within the correlation coefficient values ( R 2 ≥ 0.9993) at the concentration ranges tested. The precision of the assay method was high-performance liquid chromatography with electrospray ionization triple quadrupole mass spectrometryThe presented method was successfully applied to the quality control of eight batches of commercially available samples of Noni juiceThis method is simple, sensitive, reliable, accurate, and efficient method with strong specificity, good precision, and high recovery rate and provides a reliable basis for quality control of Noni juice. Abbreviations used: HPLC-ESI-MS/MS: High-performance liquid chromatography with electrospray ionization triple quadrupole mass spectrometry, LOD: Limit of detection, LOQ: Limit of quantitation, S/N: Signal-to-noise ratio, RSD: Relative standard deviations, DP: Declustering potential, CE: Collision energy, MRM: Multiple reaction monitoring, RT

Electron-impact ionization of multicharged ions at ORNL: 1985--1992

International Nuclear Information System (INIS)

Gregory, D.C.; Bannister, M.E.

1994-07-01

Absolute cross sections are presented in graphs and tables for single ionization of forty-one ions, multiple ionization of four ions, and for dissociation and ionization of two molecular ions by electron impact. This memo is the third in a series of manuscripts summarizing previously published as well as unpublished ionization cross section measurements at ORNL; contents of the two previous memos are also referenced in this work. All work tabulated in this memo involved ion beams generated in the ORNL-ECR ion source and utilized the ORNL electron-ion crossed beams apparatus. Target ions range from atomic number Z = 8 (oxygen) to Z = 92 (uranium) in initial charge states from +1 to +16. Electron impact energies typically range from threshold to 1500 eV

Halogeno-substituted 2-aminobenzoic acid derivatives for negative ion fragmentation studies of N-linked carbohydrates.

Science.gov (United States)

Harvey, David J

2005-01-01

Negative ion electrospray mass spectra of high-mannose N-linked glycans derivatised with 2-aminobenzoic acids and ionised from solutions containing ammonium hydroxide gave prominent [M-H](-) ions accompanied by weaker [M-2H](2-) ions. Fragmentation of both types of ions gave prominent singly charged glycosidic cleavage ions containing the derivatised reducing terminus and ions from the non-reducing terminus that appeared to be products of cross-ring cleavages. Differentiation of these two groups of ions was conveniently achieved in a single spectrum by use of chloro- or bromo-substituted benzoic acids in order to label ions containing the derivative with an atom with a distinctive isotope pattern. Fragmentation of the doubly charged ions gave more abundant fragments, both singly and doubly charged, than did fragmentation of the singly charged ions, but information of chain branching was masked by the appearance of prominent ions produced by internal cleavages. Copyright (c) 2005 John Wiley & Sons, Ltd.

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

Science.gov (United States)

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.

Surface negative ion production in ion sources

International Nuclear Information System (INIS)

Belchenko, Y.

1993-01-01

Negative ion sources and the mechanisms for negative ion production are reviewed. Several classes of sources with surface origin of negative ions are examined in detail: surface-plasma sources where ion production occurs on the electrode in contact with the plasma, and ''pure surface'' sources where ion production occurs due to conversion or desorption processes. Negative ion production by backscattering, impact desorption, and electron- and photo-stimulated desorption are discussed. The experimental efficiencies of intense surface negative ion production realized on electrodes contacted with hydrogen-cesium or pure hydrogen gas-discharge plasma are compared. Recent modifications of surface-plasma sources developed for accelerator and fusion applications are reviewed in detail

Hot-cavity studies for the Resonance Ionization Laser Ion Source

International Nuclear Information System (INIS)

Henares, J.L.; Lecesne, N.; Hijazi, L.; Bastin, B.; Kron, T.; Lassen, J.; Le Blanc, F.; Leroy, R.; Osmond, B.; Raeder, S.; Schneider, F.; Wendt, K.

2016-01-01

The Resonance Ionization Laser Ion Source (RILIS) has emerged as an important technique in many Radioactive Ion Beam (RIB) facilities for its reliability, and ability to ionize target elements efficiently and element selectively. GISELE is an off-line RILIS test bench to study the implementation of an on-line laser ion source at the GANIL separator facility. The aim of this project is to determine the best technical solution which combines high selectivity and ionization efficiency with small ion beam emittance and stable long term operation. The ion source geometry was tested in several configurations in order to find a solution with optimal ionization efficiency and beam emittance. Furthermore, a low work function material was tested to reduce the contaminants and molecular sidebands generated inside the ion source. First results with ZrC ionizer tubes will be presented. Furthermore, a method to measure the energy distribution of the ion beam as a function of the time of flight will be discussed.

Structure revision of hupehensis saponin F and G and characterization of new trace triterpenoid saponins from Anemone hupehensis by tandem electrospray ionization mass spectrometry.

Science.gov (United States)

Li, Fu; Liu, Xin; Tang, Minghai; Chen, Bin; Ding, Lisheng; Chen, Lijuan; Wang, Mingkui

2012-05-15

Electrospray ionization ion-trap tandem mass spectrometry (ESI-MS(n)) was first employed for reinvestigating the structures of hupehensis saponin F and G previously isolated from Anemone hupehensis in our lab. Hupehensis saponin G was determined to contain one more trisaccharide unit (Rha-(1→4)-Glc-(1→6)-Glc-), not a glucose residue, than saponin F based on their molecular weights deduced from their [M+Na](+) ions in ESI-MS spectra. The (2,4)A(4α)-ion at m/z 551.3 formed by retro-Diels-Alder (RDA) rearrangement in positive mode illustrated that the C-28 sugar chains of the two saponins were composed of trisaccharide repeating moieties with (1→4) linkages rather than (1→3) linkages. The interpretation of 2D-NMR spectra of the two compounds also confirmed the results obtained by ESI-MS(n). Moreover, from the water soluble part of A. hupehensis, two novel triterpene saponins were tentatively characterized to contain 4 and 5 (1→4)-linked above trisaccharide repeating moieties at C-28 position according to their ESI-MS(n) behaviors, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Contribution of electro-spray mass spectrometry to the study of the organic species and metal-ligand complexes in solution

International Nuclear Information System (INIS)

Berthon, L.; Piveteau, B.

2000-01-01

Electro-spray ionization mass spectrometry (ESI-MS) has quickly become a versatile method of qualitative analysis of a wide variety of species in solution. This technique (with positive and negative ionization modes) is used to analyze organic solutions in the frame of the DIAMEX process. Degraded solvent had been studied without any preliminary sample treatment (separation or derivation) and neutral complexes 'uranyl nitrate - malonamide' had been observed. (authors)

High-Performance Liquid Chromatography with Diode Array Detector and Electrospray Ionization Ion Trap Time-of-Flight Tandem Mass Spectrometry to Evaluate Ginseng Roots and Rhizomes from Different Regions.

Science.gov (United States)

Wang, Hong-Ping; Zhang, You-Bo; Yang, Xiu-Wei; Yang, Xin-Bao; Xu, Wei; Xu, Feng; Cai, Shao-Qing; Wang, Ying-Ping; Xu, Yong-Hua; Zhang, Lian-Xue

2016-05-09

Ginseng, Panax ginseng C. A. Meyer, is an industrial crop in China and Korea. The functional components in ginseng roots and rhizomes are characteristic ginsenosides. This work developed a new high-performance liquid chromatography coupled with electrospray ionization ion trap time-of-flight multistage mass spectrometry (LC-ESI-IT-TOF-MS(n)) method to identify the triterpenoids. Sixty compounds (1-60) including 58 triterpenoids were identified from the ginseng cultivated in China. Substances 1, 2, 7, 15-20, 35, 39, 45-47, 49, 55-57, 59, and 60 were identified for the first time. To evaluate the quality of ginseng cultivated in Northeast China, this paper developed a practical liquid chromatography-diode array detection (LC-DAD) method to simultaneously quantify 14 interesting ginsenosides in ginseng collected from 66 different producing areas for the first time. The results showed the quality of ginseng roots and rhizomes from different sources was different due to growing environment, cultivation technology, and so on. The developed LC-ESI-IT-TOF-MS(n) method can be used to identify many more ginsenosides and the LC-DAD method can be used not only to assess the quality of ginseng, but also to optimize the cultivation conditions for the production of ginsenosides.

MoS{sub 2}/Ag nanohybrid: A novel matrix with synergistic effect for small molecule drugs analysis by negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Zhao, Yaju, E-mail: daisy19900911@hotmail.com [State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023 (China); Deng, Guoqing, E-mail: denggqq@sina.com [Department of Polymer Science and Engineering, Nanjing University, Nanjing, 210023 (China); Liu, Xiaohui, E-mail: lcswyh@126.com [State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023 (China); Sun, Liang, E-mail: sunliang@nju.edu.cn [State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023 (China); Li, Hui, E-mail: lihui@nju.edu.cn [State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023 (China); Cheng, Quan, E-mail: quan.cheng@ucr.edu [Department of Chemistry, University of California, Riverside, CA, 92521 (United States); Xi, Kai, E-mail: xikai@nju.edu.cn [Department of Polymer Science and Engineering, Nanjing University, Nanjing, 210023 (China); Xu, Danke, E-mail: xudanke@nju.edu.cn [State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023 (China)

2016-09-21

This paper reports a facile synthesis of molybdenum disulfide nanosheets/silver nanoparticles (MoS{sub 2}/Ag) hybrid and its use as an effective matrix in negative ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The nanohybrid exerts a strong synergistic effect, leading to high performance detection of small molecule analytes including amino acids, peptides, fatty acids and drugs. The enhancement of laser desorption/ionization (LDI) efficiency is largely attributed to the high surface roughness and large surface area for analyte adsorption, better dispersibility, increased thermal conductivity and enhanced UV energy absorption as compared to pure MoS{sub 2}. Moreover, both Ag nanoparticles and the edge of the MoS{sub 2} layers function as deprotonation sites for proton capture, facilitating the charging process in negative ion mode and promoting formation of negative ions. As a result, the MoS{sub 2}/Ag nanohybrid proves to be a highly attractive matrix in MALDI-TOF MS, with desired features such as high desorption/ionization efficiency, low fragmentation interference, high salt tolerance, and no sweet-spots for mass signal. These characteristic properties allowed for simultaneous analysis of eight different drugs and quantification of acetylsalicylic acid in the spiked human serum. This work demonstrates for the first time the fabrication and application of a novel MoS{sub 2}/Ag hybrid, and provides a new platform for use in the rapid and high throughput analysis of small molecules by mass spectrometry. - Highlights: • MoS{sub 2}/Ag nanohybrid was applied as a novel matrix in negative-ion MALDI-TOF MS. • The MoS{sub 2}/Ag nanohybrid exerted synergistic effect on the detection of small molecules. • The MoS{sub 2}/Ag nanohybrid showed good signal reproducibility and low background interferences comparing to organic matrices. • MoS{sub 2}/Ag allows simultaneous analysis of multiple drugs and quantification of

The new BNL polarized negative ion source

International Nuclear Information System (INIS)

Hershcovitch, A.I.; Alessi, J.G.; DeVito, B.; Kponou, A.E.

1991-01-01

A new ground state source of negative hydrogen ions with polarized nuclei (rvec H - ) is being developed at BNL. Extensive developmental research has been aimed at improving each element of (rvec H - ) production: cold H degrees beam, spin selection and focusing magnets, and ionizer. These elements have recently been integrated into a source. A first test with the accommodator nozzle cooled only to liquid nitrogen temperatures resulted in 5 μA of H - . Tests at liquid helium temperatures are now beginning. 7 refs., 1 fig

Determination of torasemide in human plasma and its bioequivalence study by high-performance liquid chromatography with electrospray ionization tandem mass spectrometry

Directory of Open Access Journals (Sweden)

Lin Zhang

2016-04-01

Full Text Available A sensitive and selective method using high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (HPLC–ESI–MS to determine the concentration of torasemide in human plasma samples was developed and validated. Tolbutamide was chosen as the internal standard (IS. The chromatography was performed on a Gl Sciences Inertsil ODS-3 column (100 mm×2.1 mm i.d., 5.0 µm within 5 min, using methanol with 10 mM ammonium formate (60:40, v/v as mobile phase at a flow rate of 0.2 mL/min. The targeted compound was detected in negative ionization at m/z 347.00 for torasemide and 269.00 for IS. The linearity range of this method was found to be within the concentration range of 1–2500 ng/mL (r=0.9984 for torasemide in human plasma. The accuracy of this measurement was between 94.05% and 103.86%. The extracted recovery efficiency was from 84.20% to 86.47% at three concentration levels. This method was also successfully applied in pharmacokinetics and bioequivalence studies in Chinese volunteers.

Application of liquid chromatography/electrospray ionization ion trap tandem mass spectrometry for the evaluation of global nucleic acids: methylation in garden cress under exposure to CuO nanoparticles.

Science.gov (United States)

Alcazar Magana, Armando; Wrobel, Kazimierz; Corrales Escobosa, Alma Rosa; Wrobel, Katarzyna

2016-01-15

A full understanding of the biological impact of nanomaterials demands analytical procedures suitable for the detection/quantification of epigenetic changes that occur in the exposed organisms. Here, the effect of CuO nanoparticles (NPs) on global methylation of nucleic acids in Lepidium sativum was evaluated by liquid chromatography/ion trap mass spectrometry. Enhanced selectivity toward cytosine-containing nucleosides was achieved by using their proton-bound dimers formed in positive electrospray ionization (ESI(+)) as precursor ions for multiple reaction monitoring (MRM) quantification based on one or two ion transitions. Plants were exposed to CuO NPs (0-1000 mg L(-1)); nucleic acid extracts were washed with bathocuproine disulfate; nucleosides were separated on a Luna C18 column coupled via ESI(+) to an AmaZon SL mass spectrometer (Bruker Daltonics). Cytidine, 2´-deoxycytidine, 5-methylcytidine, 5-methyl-2´-deoxycytidine and 5-hydroxymethyl-2´-deoxycytidine were quantified by MRM based on MS(3) ([2M+H](+)/[M+H](+)/[M+H-132](+) or [M+H-116](+)) and MS(2) ([2M+H](+)/[M+H](+) ). Bathocuproine disulfate, added as Cu(I) complexing agent, allowed for elimination of [2M+Cu](+) adducts from the mass spectra. Poorer instrumental detection limits were obtained for MS(3) (20-120 fmol) as compared to MS(2) (9.0-41 fmol); however, two ion transitions helped to eliminate matrix effects in plant extracts. The procedure was tested by analyzing salmon sperm DNA (Sigma) and applied for the evaluation of DNA and RNA methylation in plants; in the absence of NPs, 13.03% and 0.92% methylated cytosines were found in DNA and RNA, respectively; for NPs concentration >50 mg L(-1), DNA hypomethylation was observed with respect to unexposed plants. RNA methylation did not present significant changes upon plant exposure; 5-hydroxymethyl-2´-deoxycytidine was not detected in any sample. The MRM quantification proposed here of cytosine-containing nucleosides using their proton-bound homo

Cationized phenylalanine conformations characterized by IRMPD and computation for singly and doubly charged ions

NARCIS (Netherlands)

Dunbar, R.C.; Steill, J.D.; Oomens, J.

2010-01-01

Electrospray ionization produces phenylalanine (Phe) complexes of the alkali metal ion series, plus Ag+ and Ba2+. Infrared multiple photon dissociation (IRMPD) spectroscopy using the FELIX free electron laser light source is used to characterize the conformations of the ions, in conjunction with

Generation of CsI cluster ions for mass calibration in matrix-assisted laser desorption/ionization mass spectrometry

NARCIS (Netherlands)

Lou, X.; Dongen, van J.L.J.; Meijer, E.W.

2010-01-01

A simple method was developed for the generation of cesium iodide (CsI) cluster ions up to m/z over 20,000 in matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). Calibration ions in both positive and negative ion modes can readily be generated from a single MALDI spot of CsI(3)

Chemical Profiling of Re-Du-Ning Injection by Ultra-Performance Liquid Chromatography Coupled with Electrospray Ionization Tandem Quadrupole Time-of-Flight Mass Spectrometry through the Screening of Diagnostic Ions in MSE Mode

Science.gov (United States)

Wang, Zhenzhong; Geng, Jianliang; Dai, Yi; Xiao, Wei; Yao, Xinsheng

2015-01-01

The broad applications and mechanism explorations of traditional Chinese medicine prescriptions (TCMPs) require a clear understanding of TCMP chemical constituents. In the present study, we describe an efficient and universally applicable analytical approach based on ultra-performance liquid chromatography coupled to electrospray ionization tandem quadrupole time-of-flight mass spectrometry (UPLC-ESI-Q/TOF-MS) with the MSE (E denotes collision energy) data acquisition mode, which allowed the rapid separation and reliable determination of TCMP chemical constituents. By monitoring diagnostic ions in the high energy function of MSE, target peaks of analogous compounds in TCMPs could be rapidly screened and identified. “Re-Du-Ning” injection (RDN), a eutherapeutic traditional Chinese medicine injection (TCMI) that has been widely used to reduce fever caused by viral infections in clinical practice, was studied as an example. In total, 90 compounds, including five new iridoids and one new sesquiterpene, were identified or tentatively characterized by accurate mass measurements within 5 ppm error. This analysis was accompanied by MS fragmentation and reference standard comparison analyses. Furthermore, the herbal sources of these compounds were unambiguously confirmed by comparing the extracted ion chromatograms (EICs) of RDN and ingredient herbal extracts. Our work provides a certain foundation for further studies of RDN. Moreover, the analytical approach developed herein has proven to be generally applicable for profiling the chemical constituents in TCMPs and other complicated mixtures. PMID:25875968

Comparison of Gas Chromatography-Mass Spectrometry and Gas Chromatography-Tandem Mass Spectrometry with Electron Ionization and Negative-Ion Chemical Ionization for Analyses of Pesticides at Trace Levels in Atmospheric Samples

Directory of Open Access Journals (Sweden)

Renata Raina

2008-01-01

Full Text Available A comparison of detection limits of gas chromatography-mass spectrometry (GC-MS in selected ion monitoring (SIM with gas chromatography-tandem mass spectrometry (GC-MS/MS in selected reaction monitoring (SRM mode with both electron ionization (EI and negative-ion chemical ionization (NCI are presented for over 50 pesticides ranging from organochlorines (OCs, organophosphorus pesticides (OPs and pre-emergent herbicides used in the Canadian prairies (triallate, trifluralin, ethalfluralin. The developed GC-EI/SIM, GC-NCI/SIM, and GC-NCI/SRM are suitable for the determination of pesticides in air sample extracts at concentrations <100 pg µL -1 (< 100 pg m -3 in air. No one method could be used to analyze the range of pre-emergent herbicides, OPs, and OCs investigated. In general GC-NCI/SIM provided the lowest method detection limits (MDLs commonly 2.5-10 pg µL -1 along with best confirmation (<25% RSD of ion ratio, while GC-NCI/SRM is recommended for use where added selectivity or confirmation is required (such as parathion-ethyl, tokuthion, carbofenothion. GC-EI/SRM at concentration < 100 pg µL -1 was not suitable for most pesticides. GC-EI/SIM was more prone to interference issues than NCI methods, but gave good sensitivity (MDLs 1-10 pg µL -1 for pesticides with poor NCI response (OPs: sulfotep, phorate, aspon, ethion, and OCs: alachlor, aldrin, perthane, and DDE, DDD, DDT.

Electron-impact ionization of atomic ions: Theoretical results

Energy Technology Data Exchange (ETDEWEB)

Loch, S D; Burgos, J M Munoz; Ballance, C P; Ludlow, J; Lee, T-G; Fogle, M; Pindzola, M S [Auburn University, Auburn, AL 36849 (United States); Griffin, D C [Rollins College, Winter Park, FL 32789 (United States); Yumak, A; Yavuz, I; Altun, Z, E-mail: loch@physics.auburn.ed [Marmara University, Istanbul (Turkey)

2009-11-15

A brief overview is given of theoretical results for electron-impact ionization of atoms and ions. A description is given of the main theoretical methods, along with the databases where the data are archived. It is shown that for light species, ground and metastable ionization cross sections are in reasonable agreement with experiment when non-perturbative data are used for the near neutrals and distorted wave data are used for ions greater than a few times ionized. Some discrepancies between theory and experiment still remain for systems with open d and open p subshells. The sensitivity of ionization rate coefficients to the near threshold part of the ionization cross section is shown. The role of excited states in effective ionization rate coefficients is demonstrated and recent excited state ionization cross section results for H, He, He{sup +}, B{sup 2+} and Ne are presented.

Rapid screening of basic colorants in processed vegetables through mass spectrometry using an interchangeable thermal desorption electrospray ionization source.

Science.gov (United States)

Chao, Yu-Ying; Chen, Yen-Ling; Lin, Hong-Yi; Huang, Yeou-Lih

2018-06-20

Thermal desorption electrospray ionization/mass spectrometry (TD-ESI-MS) employing a quickly interchangeable ionization source is a relatively new ambient ionization mass spectrometric technique that has had, to date, only a limited number of applications related to food safety control. With reallocation of resources, this direct-analysis technique has had wider use in food analysis when operated in dual-working mode (pretreatment-free qualitative screening and conventional quantitative confirmation) after switching to an ambient ionization source from a traditional atmospheric pressure ionization source. Herein, we describe the benefits and challenges associated with the use of a TD-ESI source to detect adulterants in processed vegetables (PVs), as a proof-of-concept for the detection of basic colorants. While TD-ESI can offer direct qualitative screening analyses for PVs with detection capabilities lower than those provided with liquid chromatography/UV detection within 30 s, the use of TD-ESI for semi-quantification is applicable only for homogeneous food matrices. Copyright © 2018 Elsevier B.V. All rights reserved.

Identification and Quantification of the Major Constituents in Egyptian Carob Extract by Liquid Chromatography?Electrospray Ionization-Tandem Mass Spectrometry

OpenAIRE

Owis, Asmaa Ibrahim; El-Naggar, El-Motaz Bellah

2016-01-01

Background: Carob - Ceratonia siliqua L., commonly known as St John's-bread or locust bean, family Fabaceae - is one of the most useful native Mediterranean trees. There is no data about the chromatography methods performed by high performance liquid chromatography (HPLC) for determining polyphenols in Egyptian carob pods. Objective: To establish a sensitive and specific liquid chromatography?electrospray ionization (ESI)-tandem mass spectrometry (MSn) methodology for the identification of th...

Electron-impact ionization of Pbq+ ions for q=1-10

International Nuclear Information System (INIS)

Loch, S.D.; Ludlow, J.A.; Pindzola, M.S.; Scheuermann, F.; Kramer, K.; Fabian, B.; Huber, K.; Salzborn, E.

2005-01-01

Theoretical calculations and experimental crossed-beam measurements are compared for electron-impact single ionization of Pb q+ ions for q=1-10. We compare with two main theoretical methods. First, we check against configuration-average distorted-wave calculations, which include both direct-ionization and indirect excitation-autoionization contributions. Second, for ion stages Pb + through to Pb 5+ , we calculate the dominant excitation-autoionization channels using level-resolved distorted-wave theory to evaluate the excitation cross sections. We find that for ion stages Pb + , Pb 2+ , and Pb 3+ , distorted-wave theory significantly overestimates the total-ionization cross section, due to an overestimation of the direct-ionization cross section from the 5d subshell. For ion stages Pb 4+ through to Pb 10+ there is good agreement between theory and experiment. We find evidence for significant metastable fraction in the ion beam of the experiment for ion stages Pb 2+ , Pb 3+ , Pb 4+ , Pb 5+ , and Pb 6+ . For ion stage Pb 3+ we find that the level-resolved distorted-wave calculation of the excitation autoionization results in a slight reduction of the configuration-average theoretical results, due to splitting of levels within the autoionizing configurations. We also investigate two semiempirical methods of calculating the direct-ionization cross sections: namely, the Lotz method and the binary encounter Bethe method. We find that both methods provide results which are significantly lower than the distorted-wave method for the 5d-subshell direct ionization of Pb + , Pb 2+ , and Pb 3+ . For the higher ion stages, both methods are lower than the distorted-wave direct-ionization cross-section results, trending towards the distorted-wave results as the ion stage increases

An Investigation of Chemical Landscapes in Aqueous Electrosprays by Tracking Oligomerization of Isoprene

KAUST Repository

Junior, Adair Gallo

2017-12-01

Electrospray ionization mass spectrometry (ESIMS) is widely used to characterize neutral and ionic species in solvents. Typically, electrical, thermal, and pneumatic potentials are applied to create electrosprays from which charged ionic species are ejected for downstream analysis by mass spectrometry. Most recently, ESIMS has been exploited to investigate ambient proton transfer reactions at air-water interfaces in real time. We assessed the validity of these experiments via complementary laboratory experiments. Specifically, we characterized the products of two reaction scenarios via ESIMS and proton nuclear magnetic resonance (1H-NMR): (i) emulsions of pH-adjusted water and isoprene (C5H8) that were mechanically agitated, and (ii) electrosprays of pH-adjusted water that were collided with gas-phase isoprene. Our experiments unambiguously demonstrate that, while isoprene does not oligomerize in emulsions, it does undergo protonation and oligomerization in electrosprays, both with and without pH-adjusted water, confirming that C-C bonds form along myriad high-energy pathways during electrospray ionization. We also compared our experimental results with some quantum mechanics simulations of isoprene molecules interacting with hydronium at different hydration levels (gas versus liquid phase). In agreement with our experiments, the kinetic barriers to protonation and oligomerization of isoprene were inaccessible under ambient conditions. Rather, the gas-phase chemistries during electrospray ionization drove the oligomerization of isoprene. Therefore, we consider that ESIMS could induce artifacts in interfacial reactions. These findings warrant a reassessment of previous reports on tracking chemistries under ambient conditions at liquid-vapor interfaces via ESIMS. Further, we took some high-speed images of electrosprays where it was possible to observe the main characteristics of the phenomena, i.e. Taylor cone, charge separation, and Coulomb fission. Finally, we took

Methylene-transfer reactions of benzylium/tropylium ions with neutral toluene studied by means of ion-trap mass spectrometry

Czech Academy of Sciences Publication Activity Database

Zins, E. L.; Pepe, C.; Schröder, Detlef

2010-01-01

Roč. 145, - (2010), s. 157-169 E-ISSN 1364-5498 Grant - others: ERC (XE) HORIZOMS AdG226373 Institutional research plan: CEZ:AV0Z40550506 Keywords : benzylium * electrospray ionization * infrared spectroscopy * ion trap * tropylium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.538, year: 2010

Electron impact ionization of highly charged lithiumlike ions

International Nuclear Information System (INIS)

Wong, K.L.

1992-10-01

Electron impact ionization cross sections can provide valuable information about the charge-state and power balance of highly charged ions in laboratory and astrophysical plasmas. In the present work, a novel technique based on x-ray measurements has been used to infer the ionization cross section of highly charged lithiumlike ions on the Livermore electron beam ion trap. In particular, a correspondence is established between an observed x ray and an ionization event. The measurements are made at one energy corresponding to approximately 2.3 times the threshold energy for ionization of lithiumlike ions. The technique is applied to the transition metals between Z=22 (titanium, Ti 19+ ) and Z=26 (iron, Fe 23+ ) and to Z=56 (barium, Ba 53+ ). The results for the transition metals, which have an estimated 17-33% uncertainty, are in good overall agreement with a relativistic distorted-wave calculation. However, less good agreement is found for barium, which has a larger uncertainty. Methods for properly accounting for the polarization in the x-ray intensities and for inferring the charge-state abundances from x-ray observations, which were developed for the ionization measurements, as well as an x-ray model that assists in the proper interpretation of the data are also presented

Atmospheric pressure chemical ionization studies of non-polar isomeric hydrocarbons using ion mobility spectrometry and mass spectrometry with different ionization techniques

Science.gov (United States)

Borsdorf, H.; Nazarov, E. G.; Eiceman, G. A.

2002-01-01

The ionization pathways were determined for sets of isomeric non-polar hydrocarbons (structural isomers, cis/trans isomers) using ion mobility spectrometry and mass spectrometry with different techniques of atmospheric pressure chemical ionization to assess the influence of structural features on ion formation. Depending on the structural features, different ions were observed using mass spectrometry. Unsaturated hydrocarbons formed mostly [M - 1]+ and [(M - 1)2H]+ ions while mainly [M - 3]+ and [(M - 3)H2O]+ ions were found for saturated cis/trans isomers using photoionization and 63Ni ionization. These ionization methods and corona discharge ionization were used for ion mobility measurements of these compounds. Different ions were detected for compounds with different structural features. 63Ni ionization and photoionization provide comparable ions for every set of isomers. The product ions formed can be clearly attributed to the structures identified. However, differences in relative abundance of product ions were found. Although corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra detected are complex and differ from those obtained with 63Ni ionization and photoionization. c. 2002 American Society for Mass Spectrometry.

Mass Spectrometric Analysis of Eight Common Chemical Explosives Using Ion Trap Mass Spectrometer

Energy Technology Data Exchange (ETDEWEB)

Park, Sehwan; Lee, Jihyeon; KIm, Jeongkwon [Chungnam National Univ., Daejeon (Korea, Republic of); Cho, Soo Gyeong; Goh, Eun Mee [Agency for Defense Development, Daejeon (Korea, Republic of); Lee, Sungman; Koh, Sungsuk [Sensor Tech Inc., Seoul (Korea, Republic of)

2013-12-15

Eight representative explosives (ammonium perchlorate (AP), ammonium nitrate (AN), trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), cyclonite (RDX), cyclotetramethylenetetranitramine (HMX), pentaerythritol tetranitrate (PETN), and hexanitrostilbene (HNS)) were comprehensively analyzed with an ion trap mass spectrometer in negative ion mode using direct infusion electrospray ionization. MS/MS experiments were performed to generate fragment ions from the major parent ion of each explosive. Explosives in salt forms such as AP or AN provided cluster parent ions with their own anions. Explosives with an aromatic ring were observed as either [M.H]{sup -} for TNT and DNT or [M]{sup ·-}. for HNS, while explosives without an aromatic ring such as RDX, HMX, and PETN were detected as an adduct ion with a formate anion, i. e., [M+HCOO]{sup -}. These findings provide a guideline for the rapid and accurate detection of explosives once portable MS instruments become more readily available.

Mass Spectrometric Analysis of Eight Common Chemical Explosives Using Ion Trap Mass Spectrometer

International Nuclear Information System (INIS)

Park, Sehwan; Lee, Jihyeon; KIm, Jeongkwon; Cho, Soo Gyeong; Goh, Eun Mee; Lee, Sungman; Koh, Sungsuk

2013-01-01

Eight representative explosives (ammonium perchlorate (AP), ammonium nitrate (AN), trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), cyclonite (RDX), cyclotetramethylenetetranitramine (HMX), pentaerythritol tetranitrate (PETN), and hexanitrostilbene (HNS)) were comprehensively analyzed with an ion trap mass spectrometer in negative ion mode using direct infusion electrospray ionization. MS/MS experiments were performed to generate fragment ions from the major parent ion of each explosive. Explosives in salt forms such as AP or AN provided cluster parent ions with their own anions. Explosives with an aromatic ring were observed as either [M.H] - for TNT and DNT or [M] ·- . for HNS, while explosives without an aromatic ring such as RDX, HMX, and PETN were detected as an adduct ion with a formate anion, i. e., [M+HCOO] - . These findings provide a guideline for the rapid and accurate detection of explosives once portable MS instruments become more readily available

Electrospray ionization mass spectrometric investigations of the complexation behavior of macrocyclic thiacrown ethers with bivalent transitional metals (Cu, Co, Ni and Zn).

Science.gov (United States)

Tsybizova, Alexandra; Tarábek, Ján; Buchta, Michal; Holý, Petr; Schröder, Detlef

2012-10-15

Heavy metals are both a problem for the environment and an important resource for industry. Their selective extraction by means of organic ligands therefore is an attractive topic. The coordination of three thiacrown ethers to late 3d-metal ions was investigated by a combination of electrospray ionization mass spectrometry (ESI-MS) and electron paramagnetic resonance (EPR). The mass spectrometric experiments were carried out in an ion trap mass spectrometer with an ESI source. Absolute binding constants were estimated by comparison with data for 18-crown-6/Na(+). EPR spectroscopy was used as a complementary method for investigating the Cu(I) /Cu(II) redox couple. The study found that thiacrown ethers preferentially bind traces of copper even at an excess of other metal ions (Co(II), Ni(II), and Zn(II)). The absolute association constants of the Cu(I) complexes were about 10(8) M(-1), and about two orders of magnitude lower for the other 3d-metal cations. The EPR spectra demonstrated that the reduction from Cu(II) to Cu(I) upon formation of the [(thiacrown)Cu](+) species takes place in solution. ESI-MS demonstrated that the three thiacrown ligands examined had high binding constants as well as good selectivities for copper(I) at low concentrations, and in the presence of other metal ions. By a combination of ESI-MS and EPR spectrometry it was shown that the reduction from Cu(II) to Cu(I) occurred in solution. Copyright © 2012 John Wiley & Sons, Ltd.

Negative-ion states

International Nuclear Information System (INIS)

Compton, R.N.

1982-01-01

In this brief review, we discuss some of the properties of atomic and molecular negative ions and their excited states. Experiments involving photon reactions with negative ions and polar dissociation are summarized. 116 references, 14 figures

Accurate mass analysis of ethanesulfonic acid degradates of acetochlor and alachlor using high-performance liquid chromatography and time-of-flight mass spectrometry

Science.gov (United States)

Thurman, E.M.; Ferrer, I.; Parry, R.

2002-01-01

Degradates of acetochlor and alachlor (ethanesulfonic acids, ESAs) were analyzed in both standards and in a groundwater sample using high-performance liquid chromatography-time-of-flight mass spectrometry with electrospray ionization. The negative pseudomolecular ion of the secondary amide of acetochlor ESA and alachlor ESA gave average masses of 256.0750??0.0049 amu and 270.0786??0.0064 amu respectively. Acetochlor and alachlor ESA gave similar masses of 314.1098??0.0061 amu and 314.1153??0.0048 amu; however, they could not be distinguished by accurate mass because they have the same empirical formula. On the other hand, they may be distinguished using positive-ion electrospray because of different fragmentation spectra, which did not occur using negative-ion electrospray.

Contact ionization ion source

International Nuclear Information System (INIS)

Hashmi, N.; Van Der Houven Van Oordt, A.J.

1975-01-01

An ion source in which an apertured or foraminous electrode having a multiplicity of openings is spaced from one or more active surfaces of an ionisation electrode, the active surfaces comprising a material capable of ionising by contact ionization a substance to be ionized supplied during operation to the active surface or surfaces comprises means for producing during operation a magnetic field which enables a stable plasma to be formed in the space between the active surface or surfaces and the apertured electrode, the field strength of the magnetic field being preferably in the range between 2 and 8 kilogauss. (U.S.)

Negative ion ESI-MS analysis of natural yellow dye flavonoids--An isotopic labelling study

Science.gov (United States)

McNab, Hamish; Ferreira, Ester S. B.; Hulme, Alison N.; Quye, Anita

2009-07-01

Flavonoids are amongst the most commonly used natural yellow colourants in paintings, as lakes, and in historical textiles as mordant dyes. In this paper, evidence from isotopically labelled substrates is used to propose negative ion electrospray collision induced decomposition mechanisms of flavones, flavonols and an isoflavone. These mechanisms include a retro-Diels-Alder fragmentation (observed for flavones and flavonols) and an M-122 fragmentation (characteristic of 3',4'-dihydroxyflavonols). In addition, the presence of a m/z 125 fragment ion is shown to be characteristic of 2'-hydroxyflavonols and an ion at m/z 149 is shown to be characteristic of 4'-hydroxyflavones. Applications of these methods are exemplified by the identification of a minor component of Dyer's camomile (Anthemis tinctoria L.) and the identification of the dye source in green threads sampled from an 18th Century Scottish tartan fragment.

Negative-ion current density dependence of the surface potential of insulated electrode during negative-ion implantation

International Nuclear Information System (INIS)

Tsuji, Hiroshi; Okayama, Yoshio; Toyota, Yoshitaka; Gotoh, Yasuhito; Ishikawa, Junzo; Sakai, Shigeki; Tanjyo, Masayasu; Matsuda, Kouji.

1994-01-01

Positive ion implantation has been utilized as the method of impurity injection in ultra-LSI production, but the problem of substrate charging cannot be resolved by conventional charge compensation method. It was forecast that by negative ion implantation, this charging problem can be resolved. Recently the experiment on the negative ion implantation into insulated electrodes was carried out, and the effect of negative ion implantation to this problem was proved. However, the dependence of charged potential on the increase of negative ion current at the time of negative ion implantation is a serious problem in large current negative ion implantation hereafter. The charged potential of insulated conductor substrates was measured by the negative ion implantation using the current up to several mA/cm 2 . The experimental method is explained. Medium current density and high current density negative ion implantation and charged potential are reported. Accordingly in negative ion implantation, if current density is optimized, the negative ion implantation without charging can be realized. (K.I.)

Indirect mechanisms in electron-impact ionization of multiply charged ions

International Nuclear Information System (INIS)

Phaneuf, R.A.; Gregory, D.C.

1986-09-01

The important role of indirect-ionization mechanisms in electron-impact ionization of multiply charged ions has been emphasized by some recent experiments conducted with the ORNL-ECR multicharged ion source. Illustrative examples of investigations of the Mg-isoelectronic and Fe-isonuclear sequences are presented and compared with the results of detailed theoretical calculations. New experimental data is also presented concerning the role of resonance effects in the ionization of Li-like O 5+ and Na-like Fe 15+ ions

Impact of tissue surface properties on the desorption electrospray ionization imaging of organic acids in grapevine stem.

Science.gov (United States)

Dong, Yonghui; Guella, Graziano; Franceschi, Pietro

2016-03-30

Desorption electrospray ionization (DESI) imaging is a fast analytical technique used to assess spatially resolved biological processes over unmodified sample surfaces. Although DESI profiling experiments have demonstrated that the properties of the sample surface significantly affect the outcomes of DESI analyses, the potential implications of these phenomena in imaging applications have not yet been explored extensively. The distribution of endogenous and exogenous organic acids in pith and out pith region of grapevine stems was investigated by using DESI imaging, ion chromatography and direct infusion methods. Several common normalization strategies to account for the surface effect, including TIC normalization, addition of the internal standard in the spray solvent and deposition of the standard over the sample surface, were critically evaluated. DESI imaging results show that, in our case, the measured distributions of these small organic acids are not consistent with their 'true' localizations within the tissues. Furthermore, our results indicate that the common normalization strategies are not able to completely compensate for the observed surface effect. Variations in the tissue surface properties across the tissue sample can greatly affect the semi-quantitative detection of organic acids. Attention should be paid when interpreting DESI imaging results and an independent analytical validation step is important in untargeted DESI imaging investigations. Copyright © 2016 John Wiley & Sons, Ltd.

Determination of clarithromycin in human plasma by liquid chromatography-electrospray ionization tandem mass spectrometry.

Science.gov (United States)

Jiang, Yao; Wang, Jiang; Li, Hao; Wang, Yingwu; Gu, Jingkai

2007-03-12

A rapid and sensitive method has been developed for the determination of clarithromycin in human plasma with liquid chromatography-tandem mass spectrometry. Clarithromycin and the internal standard, telmisartan were precipitated from the matrix (50 microl) with 200 microl acetonitrile and separated by HPLC using formic acid:10 mM ammonium acetate:methanol (1:99:400, v/v/v) as the mobile phase. The assay based on detection by electrospray positive ionization mass spectrometry in the multiple-reaction monitoring mode was finished within 2.4 min. Linearity was over the concentration range 10-5000 ng/ml with a limit of detection of 0.50 ng/ml. Intra- and inter-day precision measured as relative standard deviation were bioequivalence study of two tablet formulations of clarithromycin.

Multiplex Mass Spectrometric Imaging with Polarity Switching for Concurrent Acquisition of Positive and Negative Ion Images

Science.gov (United States)

Korte, Andrew R.; Lee, Young Jin

2013-06-01

We have recently developed a multiplex mass spectrometry imaging (MSI) method which incorporates high mass resolution imaging and MS/MS and MS3 imaging of several compounds in a single data acquisition utilizing a hybrid linear ion trap-Orbitrap mass spectrometer (Perdian and Lee, Anal. Chem. 82, 9393-9400, 2010). Here we extend this capability to obtain positive and negative ion MS and MS/MS spectra in a single MS imaging experiment through polarity switching within spiral steps of each raster step. This methodology was demonstrated for the analysis of various lipid class compounds in a section of mouse brain. This allows for simultaneous imaging of compounds that are readily ionized in positive mode (e.g., phosphatidylcholines and sphingomyelins) and those that are readily ionized in negative mode (e.g., sulfatides, phosphatidylinositols and phosphatidylserines). MS/MS imaging was also performed for a few compounds in both positive and negative ion mode within the same experimental set-up. Insufficient stabilization time for the Orbitrap high voltage leads to slight deviations in observed masses, but these deviations are systematic and were easily corrected with a two-point calibration to background ions.

Electron-ion correlation effects in ion-atom single ionization

Energy Technology Data Exchange (ETDEWEB)

Colavecchia, F.D.; Garibotti, C.R. [Centro Atomico Bariloche and Consejo Nacional de Investigaciones Cientificas y Tecnicas, 8400 San Carlos de Bariloche (Argentina); Gasaneo, G. [Departamento de Fisica, Universidad Nacional del Sur, Av. Alem 1253, 8000 Bahia Blanca (Argentina)

2000-06-28

We study the effect of electron-ion correlation in single ionization processes of atoms by ion impact. We present a distorted wave model where the final state is represented by a correlated function solution of a non-separable three-body continuum Hamiltonian, that includes electron-ion correlation as coupling terms of the wave equation. A comparison of the electronic differential cross sections computed with this model with other theories and experimental data reveals that the influence of the electron-ion correlation is more significant for low energy emitted electrons. (author). Letter-to-the-editor.

Gas chromatography coupled to atmospheric pressure ionization mass spectrometry (GC-API-MS): Review

International Nuclear Information System (INIS)

Li, Du-Xin; Gan, Lin; Bronja, Amela; Schmitz, Oliver J.

2015-01-01

Although the coupling of GC/MS with atmospheric pressure ionization (API) has been reported in 1970s, the interest in coupling GC with atmospheric pressure ion source was expanded in the last decade. The demand of a “soft” ion source for preserving highly diagnostic molecular ion is desirable, as compared to the “hard” ionization technique such as electron ionization (EI) in traditional GC/MS, which fragments the molecule in an extensive way. These API sources include atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), atmospheric pressure laser ionization (APLI), electrospray ionization (ESI) and low temperature plasma (LTP). This review discusses the advantages and drawbacks of this analytical platform. After an introduction in atmospheric pressure ionization the review gives an overview about the history and explains the mechanisms of various atmospheric pressure ionization techniques used in combination with GC such as APCI, APPI, APLI, ESI and LTP. Also new developments made in ion source geometry, ion source miniaturization and multipurpose ion source constructions are discussed and a comparison between GC-FID, GC-EI-MS and GC-API-MS shows the advantages and drawbacks of these techniques. The review ends with an overview of applications realized with GC-API-MS. - Highlights: • Atmospheric pressure ion sources (APCI, ESI, APPI, APLC etc) enable the coupling of LC-based high-end MS to GC. • APIs show advantages in selectivity and sensitivity compared with EI in GC-MS. • Accurate mass database in GC-APCI/MS is emerging as an alternative to GC-EI/MS database.

Gas chromatography coupled to atmospheric pressure ionization mass spectrometry (GC-API-MS): Review

Energy Technology Data Exchange (ETDEWEB)

Li, Du-Xin; Gan, Lin; Bronja, Amela [University of Duisburg-Essen, Applied Analytical Chemistry, Universitaetsstr. 5-7, 45141 Essen (Germany); Schmitz, Oliver J., E-mail: oliver.schmitz@uni-due.de [University of Duisburg-Essen, Applied Analytical Chemistry, Universitaetsstr. 5-7, 45141 Essen (Germany)

2015-09-03

Although the coupling of GC/MS with atmospheric pressure ionization (API) has been reported in 1970s, the interest in coupling GC with atmospheric pressure ion source was expanded in the last decade. The demand of a “soft” ion source for preserving highly diagnostic molecular ion is desirable, as compared to the “hard” ionization technique such as electron ionization (EI) in traditional GC/MS, which fragments the molecule in an extensive way. These API sources include atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), atmospheric pressure laser ionization (APLI), electrospray ionization (ESI) and low temperature plasma (LTP). This review discusses the advantages and drawbacks of this analytical platform. After an introduction in atmospheric pressure ionization the review gives an overview about the history and explains the mechanisms of various atmospheric pressure ionization techniques used in combination with GC such as APCI, APPI, APLI, ESI and LTP. Also new developments made in ion source geometry, ion source miniaturization and multipurpose ion source constructions are discussed and a comparison between GC-FID, GC-EI-MS and GC-API-MS shows the advantages and drawbacks of these techniques. The review ends with an overview of applications realized with GC-API-MS. - Highlights: • Atmospheric pressure ion sources (APCI, ESI, APPI, APLC etc) enable the coupling of LC-based high-end MS to GC. • APIs show advantages in selectivity and sensitivity compared with EI in GC-MS. • Accurate mass database in GC-APCI/MS is emerging as an alternative to GC-EI/MS database.

Negative ion sources for tandem accelerator

International Nuclear Information System (INIS)

Minehara, Eisuke

1980-08-01

Four kinds of negative ion sources (direct extraction Duoplasmatron ion source, radial extraction Penniing ion source, lithium charge exchange ion source and Middleton-type sputter ion source) have been installed in the JAERI tandem accelerator. The ion sources can generate many negative ions ranging from Hydrogen to Uranium with the exception of Ne, Ar, Kr, Xe and Rn. Discussions presented in this report include mechanisms of negative ion formation, electron affinity and stability of negative ions, performance of the ion sources and materials used for negative ion production. Finally, the author will discuss difficult problems to be overcome in order to get any negative ion sufficiently. (author)

A simple and selective method for the measurement of azadirachtin and related azadirachtoid levels in fruits and vegetables using liquid chromatography electrospray ionization tandem mass spectrometry.

Science.gov (United States)

Sarais, Giorgia; Caboni, Pierluigi; Sarritzu, Erika; Russo, Mariateresa; Cabras, Paolo

2008-05-14

Neem-based insecticides containing azadirachtin and related azadirachtoids are widely used in agriculture. Here, we report an analytical method for the rapid and accurate quantification of the insecticide azadirachtin A and B and other azadirachtoids such as salannin, nimbin, and their deacetylated analogues on tomatoes and peaches. Azadirachtoids were extracted from fruits and vegetables with acetonitrile. Using high-performance liquid chromatography/electrospray ionization tandem mass spectrometer, azadirachtoids were selectively detected monitoring the multiple reaction transitions of sodium adduct precursor ions. For azadirachtin A, calibration was linear over a working range of 1-1000 microg/L with r > 0.996. The limit of detection and limit of quantification for azadirachtin A were 0.4 and 0.8 microg/kg, respectively. The presence of interfering compounds in the peach and tomato extracts was evaluated and found to be minimal. Because of the linear behavior, it was concluded that the multiple reaction transitions of sodium adduct ions can be used for analytical purposes, that is, for the identification and quantification of azadirachtin A and B and related azadirachtoids in fruit and vegetable extracts at trace levels.

Electrospray ionizer for mass spectrometry of aerosol particles

Science.gov (United States)

He, Siqin; Hogan, Chris; Li, Lin; Liu, Benjamin Y. H.; Naqwi, Amir; Romay, Francisco

2017-09-19

A device and method are disclosed to apply ESI-based mass spectroscopy to submicrometer and nanometer scale aerosol particles. Unipolar ionization is utilized to charge the particles in order to collect them electrostatically on the tip of a tungsten rod. Subsequently, the species composing the collected particles are dissolved by making a liquid flow over the tungsten rod. This liquid with dissolved aerosol contents is formed into highly charged droplets, which release unfragmented ions for mass spectroscopy, such as time-of-flight mass spectroscopy. The device is configured to operate in a switching mode, wherein aerosol deposition occurs while solvent delivery is turned off and vice versa.

Chemical characterisation of non-defective and defective green arabica and robusta coffees by electrospray ionization-mass spectrometry (ESI-MS).

Science.gov (United States)

Mendonça, Juliana C F; Franca, Adriana S; Oliveira, Leandro S; Nunes, Marcella

2008-11-15

The coffee roasted in Brazil is considered to be of low quality, due to the presence of defective coffee beans that depreciate the beverage quality. These beans, although being separated from the non-defective ones prior to roasting, are still commercialized in the coffee trading market. Thus, it was the aim of this work to verify the feasibility of employing ESI-MS to identify chemical characteristics that will allow the discrimination of Arabica and Robusta species and also of defective and non-defective coffees. Aqueous extracts of green (raw) defective and non-defective coffee beans were analyzed by direct infusion electrospray ionization mass spectrometry (ESI-MS) and this technique provided characteristic fingerprinting mass spectra that not only allowed for discrimination of species but also between defective and non-defective coffee beans. ESI-MS profiles in the positive mode (ESI(+)-MS) provided separation between defective and non-defective coffees within a given species, whereas ESI-MS profiles in the negative mode (ESI(-)-MS) provided separation between Arabica and Robusta coffees. Copyright © 2008 Elsevier Ltd. All rights reserved.

Characterizing Peptide Neutral Losses Induced by Negative Electron-Transfer Dissociation (NETD)

Science.gov (United States)

Rumachik, Neil G.; McAlister, Graeme C.; Russell, Jason D.; Bailey, Derek J.; Wenger, Craig D.; Coon, Joshua J.

2012-01-01

We implemented negative electron-transfer dissociation (NETD) on a hybrid ion trap/Orbitrap mass spectrometer to conduct ion/ion reactions using peptide anions and radical reagent cations. In addition to sequence-informative ladders of a•- and x-type fragment ions, NETD generated intense neutral loss peaks corresponding to the entire or partial side-chain cleavage from amino acids constituting a given peptide. Thus, a critical step towards the characterization of this recently introduced fragmentation technique is a systematic study of synthetic peptides to identify common neutral losses and preferential fragmentation pathways. Examining 46 synthetic peptides with high mass accuracy and high resolution analysis permitted facile determination of the chemical composition of each neutral loss. We identified 19 unique neutral losses from 14 amino acids and three modified amino acids, and assessed the specificity and sensitivity of each neutral loss using a database of 1542 confidently identified peptides generated from NETD shotgun experiments employing high-pH separations and negative electrospray ionization. As residue-specific neutral losses indicate the presence of certain amino acids, we determined that many neutral losses have potential diagnostic utility. We envision this catalogue of neutral losses being incorporated into database search algorithms to improve peptide identification specificity and to further advance characterization of the acidic proteome. PMID:22290482

Quantitative correlations between collision induced dissociation mass spectrometry coupled with electrospray ionization or atmospheric pressure chemical ionization mass spectrometry - Experiment and theory

Science.gov (United States)

Ivanova, Bojidarka; Spiteller, Michael

2018-04-01

The problematic that we consider in this paper treats the quantitative correlation model equations between experimental kinetic and thermodynamic parameters of coupled electrospray ionization (ESI) mass spectrometry (MS) or atmospheric pressure chemical ionization (APCI) mass spectrometry with collision induced dissociation mass spectrometry, accounting for the fact that the physical phenomena and mechanisms of ESI- and APCI-ion formation are completely different. There are described forty two fragment reactions of three analytes under independent ESI- and APCI-measurements. The developed new quantitative models allow us to study correlatively the reaction kinetics and thermodynamics using the methods of mass spectrometry, which complementary application with the methods of the quantum chemistry provide 3D structural information of the analytes. Both static and dynamic quantum chemical computations are carried out. The object of analyses are [2,3-dimethyl-4-(4-methyl-benzoyl)-2,3-di-p-tolyl-cyclobutyl]-p-tolyl-methanone (1) and the polycyclic aromatic hydrocarbons derivatives of dibenzoperylen (2) and tetrabenzo [a,c,fg,op]naphthacene (3), respectively. As far as (1) is known to be a product of [2π+2π] cycloaddition reactions of chalcone (1,3-di-p-tolyl-propenone), however producing cyclic derivatives with different stereo selectivity, so that the study provide crucial data about the capability of mass spectrometry to provide determine the stereo selectivity of the analytes. This work also first provides quantitative treatment of the relations '3D molecular/electronic structures'-'quantum chemical diffusion coefficient'-'mass spectrometric diffusion coefficient', thus extending the capability of the mass spectrometry for determination of the exact 3D structure of the analytes using independent measurements and computations of the diffusion coefficients. The determination of the experimental diffusion parameters is carried out within the 'current monitoring method

Capillary filling of miniaturized sources for electrospray mass spectrometry

International Nuclear Information System (INIS)

Arscott, Steve; Gaudet, Matthieu; Brinkmann, Martin; Ashcroft, Alison E; Blossey, Ralf

2006-01-01

Capillary slot-based emitter tips are a novel tool for use in electrospray ionization-mass spectrometry of large biomolecules. We have performed a combined theoretical and experimental study of capillary filling in micron-sized slots with the aim of developing a rational design procedure for miniaturized electrospray sources, ultimately enabling the integration of ESI into laboratory-on-a-chip devices

Online Simultaneous Hydrogen/Deuterium Exchange of Multitarget Gas-Phase Molecules by Electrospray Ionization Mass Spectrometry Coupled with Gas Chromatography.

Science.gov (United States)

Jeong, Eun Sook; Cha, Eunju; Cha, Sangwon; Kim, Sunghwan; Oh, Han Bin; Kwon, Oh-Seung; Lee, Jaeick

2017-11-21

In this study, a hydrogen/deuterium (H/D) exchange method using gas chromatography-electrospray ionization/mass spectrometry (GC-ESI/MS) was first investigated as a novel tool for online H/D exchange of multitarget analytes. The GC and ESI source were combined with a homemade heated column transfer line. GC-ESI/MS-based H/D exchange occurs in an atmospheric pressure ion source as a result of reacting the gas-phase analyte eluted from GC with charged droplets of deuterium oxide infused as the ESI spray solvent. The consumption of the deuterated solvent at a flow rate of 2 μL min -1 was more economical than that in online H/D exchange methods reported to date. In-ESI-source H/D exchange by GC-ESI/MS was applied to 11 stimulants with secondary amino or hydroxyl groups. After H/D exchange, the spectra of the stimulants showed unexchanged, partially exchanged, and fully exchanged ions showing various degrees of exchange. The relative abundances corrected for naturally occurring isotopes of the fully exchanged ions of stimulants, except for etamivan, were in the range 24.3-85.5%. Methylephedrine and cyclazodone showed low H/D exchange efficiency under acidic, neutral, and basic spray solvent conditions and nonexchange for etamivan with an acidic phenolic OH group. The in-ESI-source H/D exchange efficiency by GC-ESI/MS was sufficient to determine the number of hydrogen by elucidation of fragmentation from the spectrum. Therefore, this online H/D exchange technique using GC-ESI/MS has potential as an alternative method for simultaneous H/D exchange of multitarget analytes.

Negative hydrogen ion production mechanisms

Energy Technology Data Exchange (ETDEWEB)

Bacal, M. [UPMC, LPP, Ecole Polytechnique, UMR CNRS 7648, Palaiseau (France); Wada, M. [School of Science and Engineering, Doshisha University, Kyoto 610-0321 (Japan)

2015-06-15

Negative hydrogen/deuterium ions can be formed by processes occurring in the plasma volume and on surfaces facing the plasma. The principal mechanisms leading to the formation of these negative ions are dissociative electron attachment to ro-vibrationally excited hydrogen/deuterium molecules when the reaction takes place in the plasma volume, and the direct electron transfer from the low work function metal surface to the hydrogen/deuterium atoms when formation occurs on the surface. The existing theoretical models and reported experimental results on these two mechanisms are summarized. Performance of the negative hydrogen/deuterium ion sources that emerged from studies of these mechanisms is reviewed. Contemporary negative ion sources do not have negative ion production electrodes of original surface type sources but are operated with caesium with their structures nearly identical to volume production type sources. Reasons for enhanced negative ion current due to caesium addition to these sources are discussed.

High Resolution Separations and Improved Ion Production and Transmission in Metabolomics

Energy Technology Data Exchange (ETDEWEB)

Metz, Thomas O.; Page, Jason S.; Baker, Erin Shammel; Tang, Keqi; Ding, Jie; Shen, Yufeng; Smith, Richard D.

2008-03-31

The goal of metabolomics experiments is the detection and quantitation of as many sample components as reasonably possible in order to identify “features” that can be used to characterize the samples under study. When utilizing electrospray ionization to produce ions for analysis by mass spectrometry (MS), it is imperative that metabolome sample constituents be efficiently separated prior to ion production, in order to minimize the phenomenon of ionization suppression. Similarly, optimization of the MS inlet can lead to increased measurement sensitivity. This review will focus on the role of high resolution liquid chromatography (LC) separations in conjunction with improved ion production and transmission for LC-MS-based metabolomics.

Production of rare-earth atomic negative ion beams in a cesium-sputter-type negative ion source

International Nuclear Information System (INIS)

Davis, V.T.; Covington, A.M.; Duvvuri, S.S.; Kraus, R.G.; Emmons, E.D.; Kvale, T.J.; Thompson, J.S.

2007-01-01

The desire to study negative ion structure and negative ion-photon interactions has spurred the development of ion sources for use in research and industry. The many different types of negative ion sources available today differ in their characteristics and abilities to produce anions of various species. Thus the importance of choosing the correct type of negative ion source for a particular research or industrial application is clear. In this study, the results of an investigation on the production of beams composed of negatively-charged rare-earth ions from a cylindrical-cathode-geometry, cesium-sputter-type negative ion source are presented. Beams of atomic anions have been observed for most of the first-row rare-earth elements, with typical currents ranging from hundreds of picoamps to several nanoamps

Determination of benzothiazole and benzotriazole derivates in tire and clothing textile samples by high performance liquid chromatography-electrospray ionization tandem mass spectrometry.

Science.gov (United States)

Avagyan, Rozanna; Sadiktsis, Ioannis; Thorsén, Gunnar; Östman, Conny; Westerholm, Roger

2013-09-13

A high performance liquid chromatography-tandem mass spectrometry method utilizing electrospray ionization in positive and negative mode has been developed for the separation and detection of benzothiazole and benzotriazole derivates. Ultra-sonication assisted solvent extraction of these compounds has also been developed and the overall method demonstrated on a selected clothing textile and an automobile tire sample. Matrix effects and extraction recoveries, as well as linearity and limits of detection have been evaluated. The calibration curves spanned over more than two orders of magnitude with coefficients of correlation R(2)>0.99 and the limits of detection and the limits of quantification were in the range 1.7-58pg injected and 18-140pg/g, respectively. The extraction recoveries ranged between 69% and 102% and the matrix effects between 75% and 101%. Benzothiazole and benzotriazole derivates were determined in the textile sample and benzothiazole derivatives determined in the tire sample with good analytical performance. Copyright © 2013 Elsevier B.V. All rights reserved.

[Determination of metformin hydrochloride, melamine and dicyandiamide in metformin hydrochloride preparations by tandem dual solid phase extraction cartridges-high performance liquid chromatography-electrospray ionization multi-stage mass spectrometry].

Science.gov (United States)

Zhou, Yanfen; Wang, Fanghuan; Wang, Zelan; Zhan, Haijuan; Liu, Wanyi; Meng, Zhe

2018-02-08

A method for the confirmation and quantification of metformin hydrochloride and its relative substances melamine and dicyandiamide using tandem dual solid phase extraction (SPE) cartridges and high performance liquid chromatography-electrospray ionization multi-stage mass spectrometry (HPLC-ESI-MS n ) was developed. The samples were extracted with anhydrous ethanol containing 0.1% (v/v) acetic acid under ultrasound-assisted conditions. The extracts were concentrated and purified using Cleanert PCX and C18 tandem dual solid phase extraction cartridges, and eluted with 5% (v/v) ammonia methanol solution. The separation was performed on a Kromasil-C18 column (100 mm×4.6 mm, 3.5 μm) with gradient elution. The detection was performed in selected ion monitoring (SIM) mode using electrospray ionization multi-stage mass spectrometry. The external standard method was used for quantification. The extraction solvents, types of SPE cartridges and eluents were optimized by comparing the recoveries under different conditions. The results showed that the detector response of each target compound was linear in corresponding mass concentration ranges with the correlation coefficients ( r 2 ) ≥ 0.9992. The limits of detection (LODs) and the limits of quantification (LOQs) of the three analytes were 1.48-13.61 μg/kg and 5.96-45.67 μg/kg, respectively. The recoveries of the three analytes were 65.02%-118.33% spiked at low, medium and high levels. The relative standard deviations (RSDs) were no more than 13.41%. The method is reliable, easy, and has a better purification effect. The method can be applied to the routine analysis of metformin hydrochloride and its relative substances melamine and dicyandiamide in different preparations of metformin hydrochloride.

A Novel Microwave-Induced Plasma Ionization Source for Ion Mobility Spectrometry

Science.gov (United States)

Dai, Jianxiong; Zhao, Zhongjun; Liang, Gaoling; Duan, Yixiang

2017-03-01

This work demonstrates the application of a novel microwave induced plasma ionization (MIPI) source to ion mobility spectrometry (IMS). The MIPI source, called Surfatron, is composed of a copper cavity and a hollow quartz discharge tube. The ion mobility spectrum of synthetics air has a main peak with reduced mobility of 2.14 cm2V-1s-1 for positive ion mode and 2.29 cm2V-1s-1 for negative ion mode. The relative standard deviations (RSD) are 0.7% and 1.2% for positive and negative ion mode, respectively. The total ion current measured was more than 3.5 nA, which is much higher than that of the conventional 63Ni source. This indicates that a better signal-to-noise ratio (SNR) can be acquired from the MIPI source. The SNR was 110 in the analysis of 500 pptv methyl tert-butyl ether (MTBE), resulting in the limit of detection (SNR = 3) of 14 pptv. The linear range covers close to 2.5 orders of magnitude in the detection of triethylamine with a concentration range from 500 pptv to 80 ppbv. Finally, this new MIPI-IMS was used to detect some volatile organic compounds, which demonstrated that the MIPI-IMS has great potential in monitoring pollutants in air.

Ion source techniques for high-speed processing of material surface by ion beams

International Nuclear Information System (INIS)

Ishikawa, Junzo

1990-01-01

The present paper discusses some key or candidate techniques for future ion source development and such ion sources developed by the author. Several types of microwave ion sources for producing low charge state ions have been developed in Japan. When a microwave plasma cathode developed by the author is adapted to a Kaufman type ion source, the electron emission currents are found to be 2.5 A for argon gas and 0.5-0.9 A for oxygen gas. An alternative ionization method for metal atoms is strongly required for high-speed processing of material surface by metal-ion beams. Detailed discussion is made of collisional ionization of vaporized atoms, and negative-ion production (secondary negative-ion emission by sputtering). An impregnated electrode type liquid-metal ion source developed by the author, which has a porous tip structure, is described. The negative-ion production efficiency is quite high. The report also presents a neutral and ionized alkaline-metal bombardment type heavy negative-ion source, which consists of a cesium plasma ion source, suppressor, target electrode, negative-ion extraction electrode, and einzel lens. (N.K.)

Negative ion detachment processes

International Nuclear Information System (INIS)

Champion, R.L.; Doverspike, L.D.

1990-10-01

This paper discusses the following topics: H - and D - collisions with atomic hydrogen; collisional decomposition of SF 6 - ; two-electron loss processes in negative ion collisions; associative electron detachment; and negative ion desorption from surfaces

Characterisation of tryptic peptides of phosphorylated tyrosine hydroxylase by high-pressure liquid chromatography electrospray ionisation mass spectrometry

International Nuclear Information System (INIS)

Graham, Mark E.; Dickson, Phillip W.; Dunkley, Peter R.; Nagy-Felsobuki, Ellak I. von

2005-01-01

Tyrosine hydroxylase (TH) is involved in the biosynthesis of catecholamines and is activated by phosphorylation. Phosphorylated TH was analysed using high-pressure liquid chromatography combined with electrospray mass spectrometry (HPLC ESI-MS). Two mass scanning methods were used to detect tryptic cleavage products of TH. In the positive electrospray ionisation mode (ESI+), the peptides that contain the phosphorylation sites of TH were identified. In the alternative method, a phosphopeptide was detected in the negative electrospray ionisation mode (ESI-) using single ion monitoring in combination with a sequential ESI+ switching experiment. A raised baseline interfered with detection of hydrophilic peptides in ESI-, with the signal-to-noise ratio indicating that the method was operating near the limit of detection for a conventional electrospray source. The switching method improved the certainty of identification of phosphopeptides

Resonance ionization laser ion sources for on-line isotope separators (invited)

International Nuclear Information System (INIS)

Marsh, B. A.

2014-01-01

A Resonance Ionization Laser Ion Source (RILIS) is today considered an essential component of the majority of Isotope Separator On Line (ISOL) facilities; there are seven laser ion sources currently operational at ISOL facilities worldwide and several more are under development. The ionization mechanism is a highly element selective multi-step resonance photo-absorption process that requires a specifically tailored laser configuration for each chemical element. For some isotopes, isomer selective ionization may even be achieved by exploiting the differences in hyperfine structures of an atomic transition for different nuclear spin states. For many radioactive ion beam experiments, laser resonance ionization is the only means of achieving an acceptable level of beam purity without compromising isotope yield. Furthermore, by performing element selection at the location of the ion source, the propagation of unwanted radioactivity downstream of the target assembly is reduced. Whilst advances in laser technology have improved the performance and reliability of laser ion sources and broadened the range of suitable commercially available laser systems, many recent developments have focused rather on the laser/atom interaction region in the quest for increased selectivity and/or improved spectral resolution. Much of the progress in this area has been achieved by decoupling the laser ionization from competing ionization processes through the use of a laser/atom interaction region that is physically separated from the target chamber. A new application of gas catcher laser ion source technology promises to expand the capabilities of projectile fragmentation facilities through the conversion of otherwise discarded reaction fragments into high-purity low-energy ion beams. A summary of recent RILIS developments and the current status of laser ion sources worldwide is presented

A resonant ionization laser ion source at ORNL

Energy Technology Data Exchange (ETDEWEB)

Liu, Y.; Stracener, D.W.

2016-06-01

Multi-step resonance laser ionization has become an essential tool for the production of isobarically pure radioactive ion beams at the isotope separator on-line (ISOL) facilities around the world. A resonant ionization laser ion source (RILIS) has been developed for the former Holifield Radioactive Ion Beam Facility (HRIBF) of Oak Ridge National Laboratory. The RILIS employs a hot-cavity ion source and a laser system featuring three grating-tuned and individually pumped Ti:Sapphire lasers, especially designed for stable and simple operation. The RILIS has been installed at the second ISOL production platform of former HRIBF and has successfully provided beams of exotic neutron-rich Ga isotopes for beta decay studies. This paper reports the features, advantages, limitations, and on-line and off-line performance of the RILIS.

Target-ion source unit ionization efficiency measurement by method of stable ion beam implantation

CERN Document Server

Panteleev, V.N; Fedorov, D.V; Moroz, F.V; Orlov, S.Yu; Volkov, Yu.M

The ionization efficiency is one of the most important parameters of an on-line used target-ion source system exploited for production of exotic radioactive beams. The ionization efficiency value determination as a characteristic of a target-ion source unit in the stage of its normalizing before on-line use is a very important step in the course of the preparation for an on-line experiment. At the IRIS facility (Petersburg Nuclear Physics Institute, Gatchina) a reliable and rather precise method of the target-ion source unit ionization efficiency measurement by the method of stable beam implantation has been developed. The method worked out exploits an off-line mass-separator for the implantation of the ion beams of selected stable isotopes of different elements into a tantalum foil placed inside the Faraday cup in the focal plane of the mass-separator. The amount of implanted ions has been measured with a high accuracy by the current integrator connected to the Faraday cup. After the implantation of needed a...

Generation of monoenergetic ion beams via ionization dynamics (Conference Presentation)

Science.gov (United States)

Lin, Chen; Kim, I. Jong; Yu, Jinqing; Choi, Il Woo; Ma, Wenjun; Yan, Xueqing; Nam, Chang Hee

2017-05-01

The research on ion acceleration driven by high intensity laser pulse has attracted significant interests in recent decades due to the developments of laser technology. The intensive study of energetic ion bunches is particularly stimulated by wide applications in nuclear fusion, medical treatment, warm dense matter production and high energy density physics. However, to implement such compact accelerators, challenges are still existing in terms of beam quality and stability, especially in applications that require higher energy and narrow bandwidth spectra ion beams. We report on the acceleration of quasi-mono-energetic ion beams via ionization dynamics in the interaction of an intense laser pulse with a solid target. Using ionization dynamics model in 2D particle-in-cell (PIC) simulations, we found that high charge state contamination ions can only be ionized in the central spot area where the intensity of sheath field surpasses their ionization threshold. These ions automatically form a microstructure target with a width of few micron scale, which is conducive to generate mono-energetic beams. In the experiment of ultraintense (< 10^21 W/cm^2) laser pulses irradiating ultrathin targets each attracted with a contamination layer of nm-thickness, high quality < 100 MeV mono-energetic ion bunches are generated. The peak energy of the self-generated micro-structured target ions with respect to different contamination layer thickness is also examined This is relatively newfound respect, which is confirmed by the consistence between experiment data and the simulation results.

Techniques for the detection of photodesorbed negative ions

International Nuclear Information System (INIS)

Young, C.E.; Schweitzer, E.L.; Pellin, M.J.; Gruen, D.M.; Hurych, Z.; Soukiassian, P.; Bakshi, M.H.; Bommannavar, A.S.

1987-01-01

This paper reports the direct observation of H - ions released from a Cs-dosed W(100) crystal by photon-stimulated desorption (PSD). This study utilized the 3m toroidal grating monochromator beamline at the University of Wisconsin-Madison Synchrotron Radiation Center. The main technical problem to be overcome in such experiments is the large background from photoemitted electrons which dominate the weak anion signal by many orders of magnitude. The solution ultimately employed utilized both magnetic suppression of photoelectrons and time-of-flight (TOF) mass separation. No internal modifications to the basic cylindrical mirror analyzer (CMA) were required. We are not aware of any previous reports of the detection of negative ions released from surfaces via photon bombardment, with the exception of high flux laser experiments, in which plasma formation is involved in the ionization process. 16 refs., 3 figs

Chemotaxonomic markers of organic, natural, and genetically modified soybeans detected by direct infusion electrospray ionization mass spectrometry

International Nuclear Information System (INIS)

Santos, L.S.; Catharino, R.R.; Eberlin, M.N.; Tsai, S.M.

2006-01-01

The crude methanolic extracts of a single bean from samples of organic, natural or genetically modified (GM) soybeans [Glycine max. (Merrill) L.] were analyzed by direct infusion electrospray ionization mass spectrometry (ESI-MS). These extracts, containing the most polar natural products of soybeans (free aglycones, monoglucosides, diglucosides and esters including isoflavones and flavones) provide characteristic fingerprinting mass spectra owing to different proportions or sets of components. Spectra distinctiveness is confirmed by chemometric multivariate analysis of the ESIMS data, which place the three-types of beans into well-defined groups. When ESI-MS is applied, these polar components constitute therefore unique chemotaxonomic markers able to provide fast soybean typification. (author)

Simultaneous detection of low and high molecular weight carbonylated compounds derived from lipid peroxidation by electrospray ionization-tandem mass spectrometry.

Science.gov (United States)

Milic, Ivana; Hoffmann, Ralf; Fedorova, Maria

2013-01-02

Reactive oxygen species (ROS) and other oxidative agents such as free radicals can oxidize polyunsaturated fatty acids (PUFA) as well as PUFA in lipids. The oxidation products can undergo consecutive reactions including oxidative cleavages to yield a chemically diverse group of products, such as lipid peroxidation products (LPP). Among them are aldehydes and ketones ("reactive carbonyls") that are strong electrophiles and thus can readily react with nucleophilic side chains of proteins, which can alter the protein structure, function, cellular distribution, and antigenicity. Here, we report a novel technique to specifically derivatize both low molecular and high molecular weight carbonylated LPP with 7-(diethylamino)coumarin-3-carbohydrazide (CHH) and analyze all compounds by electrospray ionization-mass spectrometry (ESI-MS) in positive ion mode. CHH-derivatized compounds were identified by specific neutral losses or fragment ions. The fragment ion spectra displayed additional signals that allowed unambiguous identification of the lipid, fatty acids, cleavage sites, and oxidative modifications. Oxidation of docosahexaenoic (DHA, 22:6), arachidonic (AA, 20:4), linoleic (LA, 18:2), and oleic acids (OA, 18:1) yielded 69 aliphatic carbonyls, whose structures were all deduced from the tandem mass spectra. When four phosphatidylcholine (PC) vesicles containing the aforementioned unsaturated fatty acids were oxidized, we were able to deduce the structures of 122 carbonylated compounds from the tandem mass spectra of a single shotgun analysis acquired within 15 min. The high sensitivity (LOD ∼ 1 nmol/L for 4-hydroxy-2-nonenal, HNE) and a linear range of more than 3 orders of magnitude (10 nmol/L to 10 μmol/L for HNE) will allow further studies on complex biological samples including plasma.

Modulation instability and dissipative rogue waves in ion-beam plasma: Roles of ionization, recombination, and electron attachment

Energy Technology Data Exchange (ETDEWEB)

Guo, Shimin, E-mail: gsm861@126.com; Mei, Liquan, E-mail: lqmei@mail.xjtu.edu.cn [School of Mathematics and Statistics, Xi' an Jiaotong University, Xi' an 710049 (China)

2014-11-15

The amplitude modulation of ion-acoustic waves is investigated in an unmagnetized plasma containing positive ions, negative ions, and electrons obeying a kappa-type distribution that is penetrated by a positive ion beam. By considering dissipative mechanisms, including ionization, negative-positive ion recombination, and electron attachment, we introduce a comprehensive model for the plasma with the effects of sources and sinks. Via reductive perturbation theory, the modified nonlinear Schrödinger equation with a dissipative term is derived to govern the dynamics of the modulated waves. The effect of the plasma parameters on the modulation instability criterion for the modified nonlinear Schrödinger equation is numerically investigated in detail. Within the unstable region, first- and second-order dissipative ion-acoustic rogue waves are present. The effect of the plasma parameters on the characteristics of the dissipative rogue waves is also discussed.

Observing the real time formation of phosphine-ligated gold clusters by electrospray ionization mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Ligare, Marshall R.; Johnson, Grant E.; Laskin, Julia

2017-01-01

Early stages of the reduction and nucleation of solution-phase gold clusters are largely unknown. This is due, in part, to the high reaction rates and the complexity of the cluster synthesis process. Through the addition of a diphosphine ligand, 1-4,Bis(diphenylphosphino)butane (L4) to the gold precursor, chloro(triphenylphosphine) gold(I) (Au(PPh3)Cl), in methanol organometallic complexes of the type, [Au(L4)x(L4O)y(PPh3)z]+, are formed. These complexes lower the rate of reduction so that the reaction can be directly monitored from 1 min to over an hour using on-line electrospray ionization mass spectrometry (ESI-MS). Our results indicate that the formation of Au8(L4)42+, Au9(L4)4H2+ and Au10(L4)52+ cationic clusters occurs through different reaction pathways that may be kinetically controlled either through the reducing agent concentration or the extent of oxidation of L4. Through comparison of selected ion chronograms our results indicate that Au2(L4)2H+ may be an intermediate in the formation of Au8(L4)42+and Au10(L4)52+ while a variety of chlorinated clusters are involved in the formation of Au9(L4)4H2+. Additionally, high-resolution mass spectrometry was employed to identify 53 gold containing species produced under highly oxidative conditions. New intermediate species are identified which help understand how different gold cluster nuclearities can be stabilized during the growth process.

New excitation and ionization mechanism of ions in dense plasmas

International Nuclear Information System (INIS)

Fujimoto, Takashi; Kato, Takako.

1981-10-01

It is shown that, in dense plasmas, dielectronic capture into doubly excited ionic states followed by the ladder-like excitation-ionization chain becomes important in the excitation-ionization process of ions. For an example of a hydrogen-like ion, its contribution to the excitation 1s → 2s, 2p and also to the ionization has been evaluated by the method of the quasi-steady-state solution to the rate equations. The increase is found to be substantial, i.e., by more than a factor of two both for the excitation and ionization rate coefficients. PACS classification: 52.25., 32.80.D sub(z), 34.80.D. (author)

Detection of negative ions in glow discharge mass spectrometry for analysis of solid specimens

DEFF Research Database (Denmark)

Canulescu, Stela; Molchan, Igor S.; Tauziede, C.

2010-01-01

A new method is presented for elemental and molecular analysis of halogen-containing samples by glow discharge time-of-flight mass spectrometry, consisting of detection of negative ions from a pulsed RF glow discharge in argon. Analyte signals are mainly extracted from the afterglow regime...... be used to study the distribution of a tantalum fluoride layer within the anodized tantala layer. Further, comparison is made with data obtained using glow-discharge optical emission spectroscopy, where elemental fluorine can only be detected using a neon plasma. The ionization mechanisms responsible...... for the formation of negative ions in glow discharge time-of-flight mass spectrometry are briefly discussed....

A model for negative ion extraction and comparison of negative ion optics calculations to experimental results

International Nuclear Information System (INIS)

Pamela, J.

1990-10-01

Negative ion extraction is described by a model which includes electron diffusion across transverse magnetic fields in the sheath. This model allows a 2-Dimensional approximation of the problem. It is used to introduce electron space charge effects in a 2-D particle trajectory code, designed for negative ion optics calculations. Another physical effect, the stripping of negative ions on neutral gas atoms, has also been included in our model; it is found to play an important role in negative ion optics. The comparison with three sets of experimental data from very different negative ion accelerators, show that our model is able of accurate predictions

Recent negative ion source developments

International Nuclear Information System (INIS)

Alton, G.D.

1978-01-01

This report describes recent results obtained from studies associated with the development of negative ion sources which utilize sputtering in a diffuse cesium plasma as a means of ion beam generation. Data are presented which relate negative ion yield and important operational parameters such as cesium oven temperature and sputter probe voltage from each of the following sources: (1) A source based in principle according to the University of Aarhus design and (2) an axial geometry source. The important design aspects of the sources are given--along with a list of the negative ion intensities observed to date. Also a qualitative description and interpretation of the negative ion generation mechanism in sources which utilize sputtering in the presence of cesium is given

Survey of experimental and theoretical electron-impact ionization cross sections for transition metal ions in low stages of ionization

International Nuclear Information System (INIS)

Pindzola, M.S.; Griffin, D.C.; Bottcher, C.

1985-03-01

Electron-ion crossed beams measurements and distorted-wave theory have been employed to make a study of electron-impact ionization for transition metal ions in low stages of ionization. The atomic ions Ti+, Ti 2 +, Ti 3 +, Fe+, Fe 2 +, Fe 3 +, Fe 4 +, Ni+, Ni 2 +, Ni 3 +, Cu+, Cu 2 +, and Cu 3 + are examined

Turnover rates in microorganisms by laser ablation electrospray ionization mass spectrometry and pulse-chase analysis

Energy Technology Data Exchange (ETDEWEB)

Stopka, Sylwia A.; Mansour, Tarek R.; Shrestha, Bindesh [Department of Chemistry, W.M. Keck Institute for Proteomics Technology and Applications, The George Washington University, Washington, DC 20052 (United States); Maréchal, Éric; Falconet, Denis [Laboratoire de Physiologie Cellulaire et Végétale, UMR 5168, CEA-CNRS-INRA-Univ. Grenoble Alpes, Grenoble (France); Vertes, Akos, E-mail: vertes@gwu.edu [Department of Chemistry, W.M. Keck Institute for Proteomics Technology and Applications, The George Washington University, Washington, DC 20052 (United States)

2016-01-01

Biochemical processes rely on elaborate networks containing thousands of compounds participating in thousands of reaction. Rapid turnover of diverse metabolites and lipids in an organism is an essential part of homeostasis. It affects energy production and storage, two important processes utilized in bioengineering. Conventional approaches to simultaneously quantify a large number of turnover rates in biological systems are currently not feasible. Here we show that pulse-chase analysis followed by laser ablation electrospray ionization mass spectrometry (LAESI-MS) enable the simultaneous and rapid determination of metabolic turnover rates. The incorporation of ion mobility separation (IMS) allowed an additional dimension of analysis, i.e., the detection and identification of isotopologs based on their collision cross sections. We demonstrated these capabilities by determining metabolite, lipid, and peptide turnover in the photosynthetic green algae, Chlamydomonas reinhardtii, in the presence of {sup 15}N-labeled ammonium chloride as the main nitrogen source. Following the reversal of isotope patterns in the chase phase by LAESI-IMS-MS revealed the turnover rates and half-lives for biochemical species with a wide range of natural concentrations, e.g., chlorophyll metabolites, lipids, and peptides. For example, the half-lives of lyso-DGTS(16:0) and DGTS(18:3/16:0), t{sub 1/2} = 43.6 ± 4.5 h and 47.6 ± 2.2 h, respectively, provided insight into lipid synthesis and degradation in this organism. Within the same experiment, half-lives for chlorophyll a, t{sub 1/2} = 24.1 ± 2.2 h, and a 2.8 kDa peptide, t{sub 1/2} = 10.4 ± 3.6 h, were also determined. - Highlights: • High-throughput pulse-chase analysis using direct sampling of biological cells. • Ion mobility separation for the elucidation of isotopologs. • Identification of isotopologs in difference heat plots of DT vs. m/z. • Simultaneous determination of turnover rates for lipids and

Projectile ionization in fast heavy-ion--atom collisions

International Nuclear Information System (INIS)

Schneider, D.; Prost, M.; Stolterfoht, N.; Nolte, G.; Du Bois, R.

1983-01-01

Electron emission following the ionization of projectile ions has been investigated systematically in collisions with Ne/sup q/+ and Ar/sup q/+ ions at several hundred MeV incident on different target gases. The projectile electrons are concentrated within one maximum, the electron-loss peak (ELP). The variation of the shape and intensity of the ELP with the projectile energy, its charge state, the observation angle, and the target gas has been measured. Theoretical predictions which are based on the binary-encounter approximation show, in general, good agreement with the experimental data. The contributions of the different subshells to the ELP are deduced. It is shown that electronic screening of the target nucleus plays an important role in the ionization process of the projectile ions

High intensity negative proton beams from a SNICS ion source

International Nuclear Information System (INIS)

Evans, C.R.; Hollander, M.G.

1991-01-01

For the past year we have been involved in a project to develop an intense (> 100μA) negative proton beam from a SNICS (Source of Negative Ions by Cesium Sputtering) ion source. This report will cover how we accomplished and exceeded this goal by more than 40%. Included in these observations will be the following: A description of an effective method for making titanium hydride cathodes. How to overcome the limitations of the titanium hydride cathode. The modification of the SNICS source to improve output; including the installation of the conical ionizer and the gas cathode. A discussion of problems including: poisoning the proton beam with oxygen, alternative gas cathode materials, the clogging of the gas inlet, long burn-in times, and limited cathode life times. Finally, how to optimize source performance when using a gas cathode, and what is the mechanism by which a gas cathode operates; facts, fantasies, or myth

Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling

Science.gov (United States)

Duncan, Kyle D.; Volmer, Dietrich A.; Gill, Chris G.; Krogh, Erik T.

2016-03-01

Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M - H]-) ions with limited selective fragmentation. However, carboxylates cationized with Ba2+ have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M - H + Ba]+ precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH]+ and [BaOH]+). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization.

Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling.

Science.gov (United States)

Duncan, Kyle D; Volmer, Dietrich A; Gill, Chris G; Krogh, Erik T

2016-03-01

Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M - H](-)) ions with limited selective fragmentation. However, carboxylates cationized with Ba(2+) have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M - H + Ba](+) precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH](+) and [BaOH](+)). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization.

Negative Ion Source Development and Photodetachment Studies at ISOLDE

CERN Document Server

AUTHOR|(CDS)2254068; Hanstorp, Dag; Rothe, Sebastian

Astatine is one of the rarest elements on earth. The small amount of existing astatine is either created in decay chains of heavier elements or artificially. One of its longer lived isotopes, 211At, is of interest for targeted alpha therapy, a method of treating cancer by using the alpha decay of radioactive elements directly at the location of a tumor. However, its chemical properties are yet to be determined due to the short life time of astatine. A milestone towards the determination of the electronegativity of astatine was the measurement of its ionization potential (IP) at CERN-ISOLDE. However, its electron affinity (EA, the binding energy of the additional electron in a negative ion), is still to be measured. In order to determine the EA of radioisotopes by laser photodetachment spectroscopy, the Gothenburg ANion Detector for Affinity measurements by Laser Photodetachment (GANDALPH) has been built in recent years. As a proof-of-principle, the EA of the 128I negative ion, produced at the CERN-ISOLDE rad...

Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

Science.gov (United States)

Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

2014-05-06

A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs.

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

DEFF Research Database (Denmark)

Li, Bin; Baden, Camilla Knudsen; Hansen, Natascha Kristine Krahl

2013-01-01

In comparison to 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 can be used to accurately image the distribution of even labile plant metabolites such as hydroxynitrile glucosides, which normally undergo enzymatic hydrolysis by specific ß......-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 wildtype Lotus japonicus and a ß-glucosidase mutant plant lacking the ability to hydrolyze certain hydroxynitrile...

Ion collection efficiency of ionization chambers in electron beams

International Nuclear Information System (INIS)

Garcia, S.; Cecatti, E.R.

1984-01-01

When ionization chambers are used in pulsed radiation beams the high-density of ions produced per pulse permits ion recombination, demanding the use of a correction factor. An experimental technique using the charge collected at two different voltages permits the calculation of the ion collection efficiency. The ion collection efficiency of some common ionization chambers in pulsed electron beams were studied as a function of electron energy, dose rate and depth. Accelerators with magnetic scanning system, in which the instantaneous dose rate is much greater than the average dose rate, present a smaller collection efficiency than accelerators with scattering foil. The results lead to the introduction of a correction factor for ion recombination that is the reciprocal of the ion collection efficiency. It is also suggested a simple technique to connect an external variable DC power supply in a Baldwin Farmer dosemeter. (Author) [pt

Measurements of scattering processes in negative ion-atom collisions

International Nuclear Information System (INIS)

Kvale, T.J.

1992-01-01

This Technical Progress Report describes the progress made on the research objectives during the past twelve months. This research project is designed to provide measurements of various scattering processes which occur in H - collisions with atomic (specifically, noble gas and atomic hydrogen) targets at intermediate energies. These processes include: elastic scattering,single- and double-electron detachment, and target excitation/ionization. For the elastic and target inelastic processes where H - is scattered intact, the experimental technique of Ion Energy-Loss Spectroscopy (IELS) will be employed to identify the final target state(s). In most of the above processes, cross sections are unknown both experimentally and theoretically. The measurements in progress will provide either experimentally-determined cross sections or set upper limits to those cross sections. In either case, these measurements will be stringent tests of our understanding in energetic negative ion-atom collisions. This series of experiments required the construction of a new facility and the initial ion beam was accelerated through the apparatus in April 1991

Characterization of fast pyrolysis products generated from several western USA woody species

Science.gov (United States)

Jacqueline M. Jarvis; Deborah S. Page-Dumroese; Nathaniel M. Anderson; Yuri Corilo; Ryan P. Rodgers

2014-01-01

Woody biomass has the potential to be utilized at an alternative fuel source through its pyrolytic conversion. Here, fast pyrolysis bio-oils derived from several western USA woody species are characterized by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to determine molecular-level composition. The...

SM-1 negative ion source

International Nuclear Information System (INIS)

Huang Zhenjun; Wang Jianzhen

1987-01-01

The working principle and characteristics of SM-1 Negative Ion Source is mainly introduced. In the instrument, there is a device to remove O 3 . This instrument can keep high density of negative ions which is generated by the electrical coronas setting out electricity at negative high voltage and can remove the O 3 component which is harmful to the human body. The density of negative ions is higher than 2.5 x 10 6 p./cm 3 while that of O 3 components is less than 1 ppb at the distance of 50 cm from the panel of the instrument. The instrument sprays negative ions automatically without the help of electric fan, so it works noiselessly. It is widely used in national defence, industry, agriculture, forestry, stock raising, sidelines and in the places with an equipment of low density of negative ion or high concentration of O 3 components. Besides, the instrument may also be used to treat diseases, to prevent against rot, to arrest bacteria, to purify air and so on

Electron and ion transport equations in computational weakly-ionized plasmadynamics

International Nuclear Information System (INIS)

Parent, Bernard; Macheret, Sergey O.; Shneider, Mikhail N.

2014-01-01

A new set of ion and electron transport equations is proposed to simulate steady or unsteady quasi-neutral or non-neutral multicomponent weakly-ionized plasmas through the drift–diffusion approximation. The proposed set of equations is advantaged over the conventional one by being considerably less stiff in quasi-neutral regions because it can be integrated in conjunction with a potential equation based on Ohm's law rather than Gauss's law. The present approach is advantaged over previous attempts at recasting the system by being applicable to plasmas with several types of positive ions and negative ions and by not requiring changes to the boundary conditions. Several test cases of plasmas enclosed by dielectrics and of glow discharges between electrodes show that the proposed equations yield the same solution as the standard equations but require 10 to 100 times fewer iterations to reach convergence whenever a quasi-neutral region forms. Further, several grid convergence studies indicate that the present approach exhibits a higher resolution (and hence requires fewer nodes to reach a given level of accuracy) when ambipolar diffusion is present. Because the proposed equations are not intrinsically linked to specific discretization or integration schemes and exhibit substantial advantages with no apparent disadvantage, they are generally recommended as a substitute to the fluid models in which the electric field is obtained from Gauss's law as long as the plasma remains weakly-ionized and unmagnetized

Surface Ionization and Soft Landing Techniques in Mass Spectrometry

International Nuclear Information System (INIS)

Futrell, Jean H.; Laskin, Julia

2010-01-01

The advent of soft ionization techniques, notably electrospray and laser desorption ionization methods, has extended mass spectrometric methods to large molecules and molecular complexes. This both greatly expands applications of mass spectrometry and makes the activation and dissociation of complex ions an integral part of large molecule mass spectrometry. A corollary of the much greater number of internal degrees of freedom and high density of states associated with molecular complexity is that internal energies much higher than the dissociation energies for competing fragmentation processes are required for observable fragmentation in time scales sampled by mass spectrometers. This article describes the kinetics of surface-induced dissociation (SID), a particularly efficient activation method for complex ions. Two very important characteristics of SID are very rapid, sub-picosecond activation and precise control of ion internal energy by varying ion collision energy. The nature of the surface plays an important role in SID, determining both efficiency and mechanism of ion activation. Surface composition and morphology strongly influence the relative importance of competing reactions of SID, ion capture (soft-landing), surface reaction and neutralization. The important features of SID and ion soft-landing are described briefly in this review and more fully in the recommended reading list.

The ionization length in plasmas with finite temperature ion sources

Science.gov (United States)

Jelić, N.; Kos, L.; Tskhakaya, D. D.; Duhovnik, J.

2009-12-01

The ionization length is an important quantity which up to now has been precisely determined only in plasmas which assume that the ions are born at rest, i.e., in discharges known as "cold ion-source" plasmas. Presented here are the results of our calculations of the ionization lengths in plasmas with an arbitrary ion source temperature. Harrison and Thompson (H&T) [Proc. Phys. Soc. 74, 145 (1959)] found the values of this quantity for the cases of several ion strength potential profiles in the well-known Tonks-Langmuir [Phys. Rev. 34, 876 (1929)] discharge, which is characterized by "cold" ion temperature. This scenario is also known as the "singular" ion-source discharge. The H&T analytic result covers cases of ion sources proportional to exp(βΦ) with Φ the normalized plasma potential and β =0,1,2 values, which correspond to particular physical scenarios. Many years following H&T's work, Bissell and Johnson (B&J) [Phys. Fluids 30, 779 (1987)] developed a model with the so-called "warm" ion-source temperature, i.e., "regular" ion source, under B&J's particular assumption that the ionization strength is proportional to the local electron density. However, it appears that B&J were not interested in determining the ionization length at all. The importance of this quantity to theoretical modeling was recognized by Riemann, who recently answered all the questions of the most advanced up-to-date plasma-sheath boundary theory with cold ions [K.-U. Riemann, Phys. Plasmas 13, 063508 (2006)] but still without the stiff warm ion-source case solution, which is highly resistant to solution via any available analytic method. The present article is an extension of H&T's results obtained for a single point only with ion source temperature Tn=0 to arbitrary finite ion source temperatures. The approach applied in this work is based on the method recently developed by Kos et al. [Phys. Plasmas 16, 093503 (2009)].

Analyzing Internal Fragmentation of Electrosprayed Ubiquitin Ions During Beam-Type Collisional Dissociation

Science.gov (United States)

Durbin, Kenneth R.; Skinner, Owen S.; Fellers, Ryan T.; Kelleher, Neil L.

2015-05-01

Gaseous fragmentation of intact proteins is multifaceted and can be unpredictable by current theories in the field. Contributing to the complexity is the multitude of precursor ion states and fragmentation channels. Terminal fragment ions can be re-fragmented, yielding product ions containing neither terminus, termed internal fragment ions. In an effort to better understand and capitalize upon this fragmentation process, we collisionally dissociated the high (13+), middle (10+), and low (7+) charge states of electrosprayed ubiquitin ions. Both terminal and internal fragmentation processes were quantified through step-wise increases of voltage potential in the collision cell. An isotope fitting algorithm matched observed product ions to theoretical terminal and internal fragment ions. At optimal energies for internal fragmentation of the 10+, nearly 200 internal fragments were observed; on average each of the 76 residues in ubiquitin was covered by 24.1 internal fragments. A pertinent finding was that formation of internal ions occurs at similar energy thresholds as terminal b- and y-ion types in beam-type activation. This large amount of internal fragmentation is frequently overlooked during top-down mass spectrometry. As such, we present several new approaches to visualize internal fragments through modified graphical fragment maps. With the presented advances of internal fragment ion accounting and visualization, the total percentage of matched fragment ions increased from approximately 40% to over 75% in a typical beam-type MS/MS spectrum. These sequence coverage improvements offer greater characterization potential for whole proteins with no needed experimental changes and could be of large benefit for future high-throughput intact protein analysis.

The use of isoprene as a novel dopant in negative ion atmospheric pressure photoionization mass spectrometry coupled to high-performance liquid chromatography.

Science.gov (United States)

Dousty, Faezeh; O'Brien, Rob

2015-06-15

As in the case with positive ion atmospheric pressure photoionization (PI-APPI), the addition of dopants significantly improves the sensitivity of negative ion APPI (NI-APPI). However, the research on dopant-assisted-NI-APPI has been quite limited compared to the studies on dopant-assisted PI-APPI. This work presents the potential of isoprene as a novel dopant for NI-APPI. Thirteen compounds, possessing suitable gas-phase ion energetic properties in order to make stable negative ions, were selected. Dopants were continuously introduced into a tee junction prior to the ion source through a fused-silica capillary, while analytes were directly injected into the same tee. Then both were mixed with the continuous solvent from high-performance liquid chromatography (HPLC), nebulized, and entered the source. The nebulized stream was analyzed by APPI tandem quadrupole mass spectrometry in the negative ion mode. The results obtained using isoprene were compared with those obtained by using toluene as a dopant and dopant-free NI-APPI. Isoprene enhanced the ionization intensities of the studied compounds, which were found to be comparable and, in some cases, more effective than toluene. The mechanisms leading to the observed set of negative analyte ions were also discussed. Because in NI-APPI, thermal electrons, which are produced during the photoionization of a dopant, are considered the main reagent ions, both isoprene and toluene promoted the ionization of analytes through the same mechanisms, as expected. Isoprene was shown to perform well as a novel dopant for NI-APPI. Isoprene has a high photoabsorption cross section in the VUV region; therefore, its photoionization leads to a highly effective production of thermal electrons, which further promotes the ionization of analytes. In addition, isoprene is environmentally benign and less toxic compared to currently used dopants. Copyright © 2015 John Wiley & Sons, Ltd.

Bipolar Mass Spectrometry of Labile Coordination Complexes, Redox Active Inorganic Compounds, and Proteins Using a Glass Nebulizer for Sonic-Spray Ionization

Science.gov (United States)

Antonakis, Manolis M.; Tsirigotaki, Alexandra; Kanaki, Katerina; Milios, Constantinos J.; Pergantis, Spiros A.

2013-08-01

In this study, we report on the development of a novel nebulizer configuration for sonic-spray ionization (SSI) mass spectrometry (MS), more specifically for a version of SSI that is referred to as Venturi easy ambient sonic-spray ionization (V-EASI) MS. The developed nebulizer configuration is based on a commercially available pneumatic glass nebulizer that has been used extensively for aerosol formation in atomic spectrometry. In the present study, the nebulizer was modified in order to achieve efficient V-EASI-MS operation. Upon evaluating this system, it has been demonstrated that V-EASI-MS offers some distinct advantages for the analysis of coordination compounds and redox active inorganic compounds over the predominantly used electrospray ionization (ESI) technique. Such advantages, for this type of compounds, are demonstrated here for the first time. More specifically, a series of labile heptanuclear heterometallic [CuII 6LnIII] clusters held together with artificial amino acid ligands, in addition to easily oxidized inorganic oxyanions of selenium and arsenic, were analyzed. The observed advantages pertain to V-EASI appearing to be a "milder" ionization source than ESI, not requiring electrical potentials for gas phase ion formation, thus eliminating the possibility of unwanted redox transformations, allowing for the "simultaneous" detection of negative and positive ions (bipolar analysis) without the need to change source ionization conditions, and also not requiring the use of syringes and delivery pumps. Because of such features, especially because of the absence of ionization potentials, EASI can be operated with minimal requirements for source parameter optimization. We observed that source temperature and accelerating voltage do not seem to affect labile compounds to the extent they do in ESI-MS. In addition, bipolar analysis of proteins was demonstrated here by acquiring both positive and negative ion mass spectra from the same protein solutions

Space-charge-limited ion flow through an ionizing neutral layer

International Nuclear Information System (INIS)

Duvall, R.E.; Litwin, C.; Maron, Y.

1993-01-01

Space-charge-limited ion flow through an ionizing layer of neutral atoms is studied. The ion flow is between two parallel conducting plates (anode and cathode) with an externally applied voltage between them. An expanding layer of neutral atoms is adjacent to the anode surface, extending a finite distance into the anode--cathode gap. All ions originate either from the anode surface or from the ionization of neutrals; electrons originate only from ionization. Electrons are strongly magnetized by an externally applied, time-independent direct current (dc) magnetic field directed across the ion flow. The ions are unmagnetized, all motion being perpendicular to the conducting plates. Two different models of the anode layer were used to analyze this problem: a multifluid steady-state model and a single fluid time-dependent model. From both models it was found that the anode surface becomes shielded after the ion flux from the ionizing layer becomes larger than the space-charge-limited flux of the reduced gap between the neutral layer and cathode. Comparison was made between the time-dependent model and results from magnetically insulated ion beam diode (MID) experiments. Using an initial areal density of neutral hydrogen and carbon equal to the final observed electron areal density, comparison was made between calculated plasma shielding times and upper bounds on the shielding time observed in experiments. It was found that a layer of neutral hydrogen must contain a minimum of 15% carbon (by number density) to explain the rapid electric field screening observed in experiments

Reprint of: Negative carbon cluster ion beams: New evidence for the special nature of C60

Science.gov (United States)

Liu, Y.; O'brien, S. C.; Zhang, Q.; Heath, J. R.; Tittel, F. K.; Curl, R. F.; Kroto, H. W.; Smalley, R. E.

2013-12-01

Cold carbon cluster negative ions are formed by supersonic expansion of a plasma created at the nozzle of a supersonic cluster beam source by an excimer laser pulse. The observed distribution of mass peaks for the Cn- ions for n > 40 demonstrates that the evidence previously given for the special stability of neutral C60 and the existence of spheroidal carbon shells cannot be an artifact of the ionization conditions.

Successive ionization of positive ions of carbon and nitrogen by electron bombardment

International Nuclear Information System (INIS)

Donets, E.D.; Ilyushchenko, V.I.

Experimental studies of deep ionization of heavy ions are described. The applications of such studies in atomic physics, plasma physics and space physics are discussed. Investigations using intersecting ion-electron beams, shifted beams and ion trap sources are described, and data are presented for multi-charged ions of carbon, oxygen and nitrogen. A detailed description of the development of the IEL (electron beam ionizer) source, and the KRION (cryogenic version) source is given, and further data for the multiple ionization of carbon and nitrogen are given for charge states up to C 6+ and N 7+ . The advantages and disadvantages of the KRION source are discussed, and preliminary studies of a new torroidal ion trap source (HIRAC) are presented. (11 figs, 57 refs) (U.S.)

Collective ion acceleration via laser controlled ionization channel

International Nuclear Information System (INIS)

Destler, W.W.; O'Shea, P.G.; Rodgers, J.; Segalov, Z.

1987-01-01

Initial results from a successful laser-controlled collective ion acceleration experiment at the University of Maryland are presented. In the experiment, positive ions are trapped in the potential well at the head of an intense relativistic electron beam injected at current levels above the space charge limit. Seed ions for acceleration are provided by puff valve injection of a neutral gas cloud localized to within 3 cm of the injection point. Control over the acceleration of the well and the ions is then achieved by means of a laser-generated ionization channel produced by passing the light from a Q-switched ruby laser through a series of partially and fully reflecting mirrors in such a way as to provide time-sequenced laser ionization of a target located on the drift tube wall. Using this system, controlled acceleration of protons at a rate of approximately 40 MV/m has been demonstrated over a distance of about 50 cm

Formation of hydrogen negative ions by surface and volume processes with application to negative ion sources

International Nuclear Information System (INIS)

Hiskes, J.R.

1979-01-01

During the last few decades interest in negative-hydrogen ion sources has been directed mainly toward synchrotron and other particle accelerator applications, with emphasis on high current densities delivered for short pulses. But within the last several years there has been an awareness in the magnetic fusion program of the future need for negative ions as a means for generating high energy neutral beams, beams with energies above a few hundred keV. Negative ions seem to be the only effective intermediary for efficiently producing such beams. Although methods for generating negative ion beams have relied upon synchrotron concepts, the requirements for fusion are very different: here one is interested in more moderate current densities, up to 100 m A cm -2 , but with continuous operation. Proposed source modules would accelerate of the order of 10 A of beam current and deliver several megawatts of beam power. Both H - and D - beams are being considered for application in different reactor systems. The conceptualization of negative ion sources is now in a very volatile stage. But of the great variety of proposals that have been offered to date, three general areas appear ready for development. These are: first, the double charge exchange method for converting a positive ion beam into a negative ion beam; second, electron-volume processes wherein low energy electrons interacting with molecular species lead to negative ion products via dissociative attachment or recombination; and third, generation of negative ions in surface interactions, principally via desorption and backscattering. Both our qualitative and our quantitative understanding of these processes diminishes as one proceeds from the first through the third. The physics of these three methods is considered in detail

Negative Ions in low pressure discharges

NARCIS (Netherlands)

Stoffels - Adamowicz, E.; Stoffels, W.W.; Vender, D.; Haverlag, M.; Kroesen, G.M.W.; Hoog, de F.J.

1995-01-01

Several aspects of negative ions in low pressure discharges are treated. The elementary processes, in which negative ions are produced and destroyed, are summarized. The influence of negative ions on plasma operation is analyzed in terms of transport equations. It is shown that diffusion, electric

A Versatile Integrated Ambient Ionization Source Platform

Science.gov (United States)

Ai, Wanpeng; Nie, Honggang; Song, Shiyao; Liu, Xiaoyun; Bai, Yu; Liu, Huwei

2018-04-01

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. [Figure not available: see fulltext.

Resonance ionization in a gas cell: a feasibility study for a laser ion source

International Nuclear Information System (INIS)

Qamhieh, Z.N.; Vandeweert, E.; Silverans, R.E.; Duppen, P. van; Huyse, M.; Vermeeren, L.

1992-01-01

A laser ion source based on resonance photo-ionization in a gas cell is proposed. The gas cell, filled with helium, consists of a target chamber in which the recoil products are stopped and neutralized, and an ionization chamber where the atoms of interest are selectively ionized by the laser light. The extraction of the ions from the ionization chamber through the exit hole-skimmer setup is similar to the ion-guide system. The conditions to obtain an optimal system are given. The results of a two-step one-laser resonance photo-ionization of nickel and the first results of laser ionization in a helium buffer gas cell are presented. (orig.)

Comprehensive characterization of natural organic matter by MALDI- and ESI-Fourier transform ion cyclotron resonance mass spectrometry

International Nuclear Information System (INIS)

Cao, Dong; Huang, Huogao; Hu, Ming; Cui, Lin; Geng, Fanglan; Rao, Ziyu; Niu, Hongyun; Cai, Yaqi; Kang, Yuehui

2015-01-01

Highlights: • MALDI-FT-ICR-MS was firstly employed for molecular characterization of NOM. • 1,8-Bis(dimethyl-amino)-naphthalene (DMAN) was used as matrix. • Mass spectra of NOM generated by MALDI and ESI methods were compared. • Complementary molecular information of NOM was provided by MALDI. - Abstract: Natural organic matter (NOM) is a complex and non-uniform mixture of organic compounds which plays an important role in environmental processes. Due to the complexity, it is challenging to obtain fully detailed structural information about NOM. Although Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) has been demonstrated to be a powerful tool for providing molecular information about NOM, multiple ionization methods are needed for comprehensive characterization of NOM at the molecular level considering the ionizing selectivity of different ionization methods. This paper reports the first use of matrix assisted laser desorption/ionization (MALDI) method coupled with FT-ICR-MS for molecular characterization of NOM within a mass range of 200–800 Da. The mass spectral data obtained by MALDI were systematically compared with data generated by electrospray ionization (ESI). It showed that complementary molecular information about NOM which could not be detected by ESI, were provided by MALDI. More unsaturated and aromatic constituents of NOM with lower O/C ratio (O/C ratio < 0.5) were preferentially ionized in MALDI negative mode, whereas more polar constituents of NOM with higher O/C ratio were preferentially ionized in ESI negative mode. Molecular anions of NOM appearing at even m/z in MALDI negative ion mode were detected. The results show that NOM molecules with aromatic structures, moderate O/C ratio (0.7 > O/C ratio > 0.25) and lower H/C ratio were liable to form molecular anions at even m/z, whereas those with higher H/C ratio are more likely to form deprotonated ions at odd m/z. It is speculated that almost half of the NOM

Polymer Analysis by Liquid Chromatography/Electrospray Ionization Time-of-Flight Mass Spectrometry.

Science.gov (United States)

Nielen, M W; Buijtenhuijs, F A

1999-05-01

Hyphenation of liquid chromatography (LC) techniques with electrospray ionization (ESI) orthogonal acceleration time-of-flight (oa-TOF) mass spectrometry (MS) provides both MS-based structural information and LC-based quantitative data in polymer analysis. In one experimental setup, three different LC modes are interfaced with MS:  size-exclusion chromatography (SEC/MS), gradient polymer elution chromatography (GPEC/MS), and liquid chromatography at the critical point of adsorption (LCCC/MS). In SEC/MS, both absolute mass calibration of the SEC column based on the polymer itself and determination of monomers and end groups from the mass spectra are achieved. GPEC/MS shows detailed chemical heterogeneity of the polymer and the chemical composition distribution within oligomer groups. In LCCC/MS, the retention behavior is primarily governed by chemical heterogeneities, such as different end group functionalities, and quantitative end group calculations can be easily made. The potential of these methods and the benefit of time-of-flight analyzers in polymer analysis are discussed using SEC/MS of a polydisperse poly(methyl methacrylate) sample, GPEC/MS of dipropoxylated bisphenol A/adipic acid polyester resin, LCCC/MS of alkylated poly(ethylene glycol), and LCCC/MS of terephthalic acid/neopentyl glycol polyester resin.

Performance evaluation of oxygen adsorbents using negative corona discharge–ion mobility spectrometry

Energy Technology Data Exchange (ETDEWEB)

Azadkish, Kamal; Jafari, Mohammad T., E-mail: jafari@cc.iut.ac.ir; Ghaziaskar, Hassan S.

2017-02-08

Trace amounts of oxygen was determined using negative corona discharge as an ionization source for ion mobility spectrometry. A point-in-cylinder geometry with novel design was used to establish the corona discharge without interferences of negative ions such as NO{sub X}{sup −}. The desirable background spectrum shows only electrons peak, providing the instrument capable of trace analysis of oxygen in gaseous samples. The limit of detection and linear dynamic range with high coefficient of determination (r{sup 2} = 0.9997), were obtained for oxygen as 8.5 and 28–14204 ppm, respectively. The relative standard deviations of the method for intraday and interday were obtained 4 and 11%, respectively. The satisfactory results revealed the ability of the negative corona discharge ion mobility spectrometry for investigating the performance of synthesized oxygen adsorbents in nitrogen streams. Two oxygen scavengers of MnO and Cu powder were prepared and the optimum temperature of the reactor containing MnO and Cu powder were obtained as 180 and 230 °C, respectively. Due to higher lifetime of copper powder, it was selected as the oxygen scavenger and some parameters such as: the type of adsorbent support, the size of adsorbent particles, and the amount of copper were studied for preparation of more efficient oxygen adsorbent. - Highlights: • Analysis of oxygen using negative corona discharge-ion mobility spectrometry was investigated for the first time. • Novel designed point-in-cylinder geometry was used to establish the corona discharge without interferences of negative ions. • The method was utilized to evaluate the performance of some synthesized oxygen scavengers.

Quantitative Profiling of Major Neutral Lipid Classes in Human Meibum by Direct Infusion Electrospray Ionization Mass Spectrometry

Science.gov (United States)

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

2013-01-01

Purpose. The purpose of this investigation was to better understand lipid composition in human meibum. Methods. Intact lipids in meibum samples were detected by direct infusion electrospray ionization mass spectrometry (ESI-MS) analysis in positive detection mode using sodium iodide (NaI) as an additive. The peak intensities of all major types of lipid species, that is, wax esters (WEs), cholesteryl esters (CEs), and diesters (DEs) were corrected for peak overlapping and isotopic distribution; an additional ionization efficiency correction was performed for WEs and CEs, which was simplified by the observation that the corresponding ionization efficiency was primarily dependent on the specific lipid class and saturation degree of the lipids while independent of the carbon chain length. A set of WE and CE standards was spiked in meibum samples for ionization efficiency determination and absolute quantitation. Results. The absolute amount (μmol/mg) for each of 51 WEs and 31 CEs in meibum samples was determined. The summed masses for 51 WEs and 31 CEs accounted for 48 ± 4% and 40 ± 2%, respectively, of the total meibum lipids. The mass percentages of saturated and unsaturated species were determined to be 75 ± 2% and 25 ± 1% for CEs and 14 ± 1% and 86 ± 1% for WEs. The profiles for two types of DEs were also obtained, which include 42 α,ω Type II DEs, and 21 ω Type I-St DEs. Conclusions. Major neutral lipid classes in meibum samples were quantitatively profiled by ESI-MS analysis with NaI additive. PMID:23847307

Deep-down ionization of protoplanetary discs

Science.gov (United States)

Glassgold, A. E.; Lizano, S.; Galli, D.

2017-12-01

The possible occurrence of dead zones in protoplanetary discs subject to the magneto-rotational instability highlights the importance of disc ionization. We present a closed-form theory for the deep-down ionization by X-rays at depths below the disc surface dominated by far-ultraviolet radiation. Simple analytic solutions are given for the major ion classes, electrons, atomic ions, molecular ions and negatively charged grains. In addition to the formation of molecular ions by X-ray ionization of H2 and their destruction by dissociative recombination, several key processes that operate in this region are included, e.g. charge exchange of molecular ions and neutral atoms and destruction of ions by grains. Over much of the inner disc, the vertical decrease in ionization with depth into the disc is described by simple power laws, which can easily be included in more detailed modelling of magnetized discs. The new ionization theory is used to illustrate the non-ideal magnetohydrodynamic effects of Ohmic, Hall and Ambipolar diffusion for a magnetic model of a T Tauri star disc using the appropriate Elsasser numbers.

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

International Nuclear Information System (INIS)

Wang, Lai-Sheng

2015-01-01

Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES

Identification and Quantification of the Major Constituents in Egyptian Carob Extract by Liquid Chromatography–Electrospray Ionization-Tandem Mass Spectrometry

Science.gov (United States)

Owis, Asmaa Ibrahim; El-Naggar, El-Motaz Bellah

2016-01-01

Background: Carob - Ceratonia siliqua L., commonly known as St John's-bread or locust bean, family Fabaceae - is one of the most useful native Mediterranean trees. There is no data about the chromatography methods performed by high performance liquid chromatography (HPLC) for determining polyphenols in Egyptian carob pods. Objective: To establish a sensitive and specific liquid chromatography–electrospray ionization (ESI)-tandem mass spectrometry (MSn) methodology for the identification of the major constituents in Egyptian carob extract. Materials and Methods: HPLC with diode array detector and ESI-mass spectrometry (MS) was developed for the identification and quantification of phenolic acids, flavonoid glycosides, and aglycones in the methanolic extract of Egyptian C. siliqua. The MS and MSn data together with HPLC retention time of phenolic components allowed structural characterization of these compounds. Peak integration of ions in the MS scans had been used in the quantification technique. Results: A total of 36 compounds were tentatively identified. Twenty-six compounds were identified in the negative mode corresponding to 85.4% of plant dry weight, while ten compounds were identified in the positive mode representing 16.1% of plant dry weight, with the prevalence of flavonoids (75.4% of plant dry weight) predominantly represented by two methylapigenin-O-pentoside isomers (20.9 and 13.7% of plant dry weight). Conclusion: The identification of various compounds present in carob pods opens a new door to an increased understanding of the different health benefits brought about by the consumption of carob and its products. SUMMARY This research proposed a good example for the rapid identification of major constituents in complex systems such as herbs using sensitive, accurate and specific method coupling HPLC with DAD and MS, which facilitate the clarification of phytochemical composition of herbal medicine for better understanding of their nature and

Establishment of a Charge Reversal Derivatization Strategy to Improve the Ionization Efficiency of Limaprost and Investigation of the Fragmentation Patterns of Limaprost Derivatives Via Exclusive Neutral Loss and Survival Yield Method

Science.gov (United States)

Sun, Dong; Meng, Xiangjun; Ren, Tianming; Fawcett, John Paul; Wang, Hualu; Gu, Jingkai

2018-04-01

Sensitivity is generally an issue in bioassays of prostaglandins and their synthetic analogs due to their extremely low concentration in vivo. To improve the ionization efficiency of limaprost, an oral prostaglandin E1 (PGE1) synthetic analog, we investigated a charge reversal derivatization strategy in electrospray ionization mass spectrometry (ESI-MS). We established that the cholamine derivative exhibits much greater signal intensity in the positive-ion mode compared with limaprost in the negative ion mode. Collision-induced dissociation (CID) involved exclusive neutral mass loss and positive charge migration to form stable cationic product ions with the positive charge on the limaprost residue rather than on the modifying group. This has the effect of maintaining the efficiency and specificity of multiple reaction monitoring (MRM) and avoiding cross talk. CID fragmentation patterns of other limaprost derivatives allowed us to relate the dissociation tendency of different neutral leaving groups to an internal energy distribution scale based on the survival yield method. Knowledge of the energy involved in the production of stabilized positive ions will potentially assist the selection of suitable derivatization reagents for the analysis of a wide variety of lipid acids. [Figure not available: see fulltext.

Evidence for electron-based ion generation in radio-frequency ionization.

Science.gov (United States)

Olaitan, Abayomi D; Zekavat, Behrooz; Solouki, Touradj

2016-01-01

Radio-frequency ionization (RFI) is a novel ionization method coupled to mass spectrometry (MS) for analysis of semi-volatile and volatile organic compounds (VOCs). Despite the demonstrated capabilities of RFI MS for VOC analysis in both positive- and negative-ion modes, mechanism of RFI is not completely understood. Improved understanding of the ion generation process in RFI should expand its utility in MS. Here, we studied the possibility of electron emission in RFI using both direct charged particle current measurements and indirect electron detection in a 9.4-T Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer. We show that RF-generated electrons can be trapped in the ICR cell and, subsequently, reacted with neutral hexafluorobenzene (C6 F6 ) molecules to generate C6 F6 (●-) . Intensity of observed C6 F6 (●-) species correlated with the number of trapped electrons and decreased as a function of electron quenching period. We also measured the electron attachment rate constant of hexafluorobenzene using a post-RF electron trapping experiment. Measured electron attachment rate constant of hexafluorobenzene (1.19 (±0.53) × 10(-9)  cm(3)  molecule(-1)  s(-1) ) for post-RF FT-ICR MS agreed with the previously reported value (1.60 (±0.30) × 10(-9)  cm(3)  molecule(-1)  s(-1) ) from low-pressure ICR MS measurements. Experimental results from direct and indirect electron measurements suggest that RFI process involves RF-generated electrons under ultrahigh vacuum conditions. Copyright © 2015 John Wiley & Sons, Ltd.

Improved detection limits for electrospray ionization on a magnetic sector mass spectrometer by using an array detector.

Science.gov (United States)

Cody, R B; Tamura, J; Finch, J W; Musselman, B D

1994-03-01

Array detection was compared with point detection for solutions of hen egg-white lysozyme, equine myoglobin, and ubiquitin analyzed by electrospray ionization with a magnetic sector mass spectrometer. The detection limits for samples analyzed by using the array detector system were at least 10 times lower than could be achieved by using a point detector on the same mass spectrometer. The minimum detectable quantity of protein corresponded to a signal-to-background ratio of approximately 2∶1 for a 500 amol/μL solution of hen egg-white lysozyme. However, the ultimate practical sample concentrations appeared to be in the 10-100 fmol/μL range for the analysis of dilute solutions of relatively pure proteins or simple mixtures.

Electron impact ionization of heavy ions: some surprises

International Nuclear Information System (INIS)

Younger, S.M.

1986-01-01

This paper reports the results of calculations of electron impact ionization cross sections for a variety of heavy ions using a distorted wave Born-exchange approximation. The target is described by a Hartree-Fock wavefunction. The scattering matrix element is represented by a triple partial wave expansion over incident, scattered, and ejected (originally bound) continuum states. These partial waves are computed in the potentials associated with the initial target (incident and scattered waves) and the residual ion (ejected waves). A Gauss integration was performed over the distribution of energy between the two final state continuum electrons. For ionization of closed d- and f-subshells, the ejected f-waves were computed in frozen-core term-dependent Hartree-Fock potentials, which include the strong repulsive contribution in singlet terms which arises from the interaction of an excited orbital with an almost closed shell. Ground state correlation was included in some calculations of ionization of d 10 subshells

Electron-impact ionization of heavy atomic ions

International Nuclear Information System (INIS)

Pindzola, M.S.; Griffin, D.C.; Bottcher, C.

1987-01-01

General theoretical methods for the calculation of direct and indirect processes in the electron-impact ionization of heavy atomic ions are reviewed. Cross section results for Xe 8+ and U 89+ are presented. 12 refs., 4 figs

Multiple ionization and coupling effects in L-subshell ionization of heavy atoms by oxygen ions

International Nuclear Information System (INIS)

Pajek, M.; Banas, D.; Semaniak, J.; Braziewicz, J.; Majewska, U.; Chojnacki, S.; Czyzewski, T.; Fijal, I.; Jaskola, M.; Glombik, A.; Kretschmer, W.; Trautmann, D.; Lapicki, G.; Mukoyama, T.

2003-01-01

The multiple-ionization and coupling effects in L-shell ionization of atoms by heavy-ion impact have been studied by measuring the L x-ray production cross sections in solid targets of Au, Bi, Th, and U bombarded by oxygen ions in the energy range 6.4-70 MeV. The measured L x-ray spectra were analyzed using the recently proposed method accounting for the multiple-ionization effects, such as x-ray line shifting and broadening, which enables one to obtain the ionization probabilities for outer shells. The L-subshell ionization cross sections have been obtained from measured x-ray production cross sections for resolved Lα 1,2 , Lγ 1 , and Lγ 2,3 transitions using the L-shell fluorescence and Coster-Kronig yields being substantially modified by the multiple ionization in the M and N shells. In particular, the effect of closing of strong L 1 -L 3 M 4,5 Coster-Kronig transitions in multiple-ionized atoms was evidenced and discussed. The experimental ionization cross sections for the L 1 , L 2 , and L 3 subshells have been compared with the predictions of the semiclassical approximation (SCA) and the ECPSSR theory that includes the corrections for the binding-polarization effect within the perturbed stationary states approximation, the projecticle energy loss, and Coulomb deflection effects as well as the relativistic description of inner-shell electrons. These approaches were further modified to include the L-subshell couplings within the ''coupled-subshell model'' (CSM). Both approaches, when modified for the coupling effects, are in better agreement with the data. Particularly, the predictions of the SCA-CSM calculations reproduce the experimental L-subshell ionization cross section reasonably well. Remaining discrepancies are discussed qualitatively, in terms of further modifications of the L-shell decay rates caused by a change of electronic wave functions in multiple-ionized atoms

Quantitative Thin-Layer Chromatography/Mass Spectrometry Analysis of Caffeine Using a Surface Sampling Probe Electrospray Ionization Tandem Mass Spectrometry System

Energy Technology Data Exchange (ETDEWEB)

Ford, Michael J [ORNL; Deibel, Michael A. [Earlham College; Tomkins, Bruce A [ORNL; Van Berkel, Gary J [ORNL

2005-01-01

Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 {mu}m/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methods determined from the calibration curve statistics were 0.20 ng injected (0.50 {mu}L) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by 8% or more) than the literature values.

Microparticle charging in dry air plasma created by an external ionization source

International Nuclear Information System (INIS)

Derbenev, I N; Filippov, A V

2015-01-01

In the present paper the dust particle charging is studied in a dry air plasma created by an external ionization source. The ionization rate is changed in the range 10 1 -10 20 cm -3 s -1 . It is found that the main positive ion of the plasma is O + 4 and the main negative ones are O − 2 and O − 4 . The point sink model based on the diffusion-drift approach shows that the screening potential distribution around a dust particle is a superposition of four Debye-like exponentials with four different spatial scales. The first scale almost coincides with the Debye radius. The second one is the distance, passed by positive and negative plasma components due to ambipolar diffusion in their recombination time. The third one is defined by the negative ion conversion and diffusion. The fourth scale is described by the electron attachment, recombination and diffusion at low gas ionization rates and by the recombination and diffusion of negative diatomic ions at high ionization rates. It is also shown that the electron flux defines the microparticle charge at high ionization rates, whereas the electron number density is much less than the ion one. (paper)

Design considerations for a negative ion source for dc operation of high-power, multi-megaelectron-volt neutral beams

International Nuclear Information System (INIS)

Tsai, C.C.; Stirling, W.L.; Akerman, M.A.; Becraft, W.R.; Dagenhart, W.K.; Haselton, H.H.; Ryan, P.M.; Schechter, D.E.; Whealton, J.H.

1988-03-01

A dc negative hydrogen and/or deuterium ion source is needed to prouce high-power, high-energy neutral beams for alpha diagnostics and current drive applicatiosn in fusion devices. The favorable beam particle energy for such applications extends to 1.5 MeV/amu. Continuous-wave (cw) radio-frequency quadrupole (RFQ) accelerators have been proposed to accelerate negative ions effeciently to this energy range. In this paper, the desired beam properties for ion beams injected into cw RFQ accelerators are summariezed. A number of candidate ion sources being developed at Culham, JAERI, LBL, and ORNL may prove useful for these applications. The properties of the Volume Ionization with Transverse Extraction (VITEX) ion sources being developed at ORNL are presented. Scaling such a dc ion source to produce ampere beams is discussed. 53 refs., 4 figs., 2 tabs

Design considerations for a negative ion source for dc operation of high-power, multi-megaelectron-volt neutral beams

International Nuclear Information System (INIS)