Sample records for negative chemical ionization

  1. PULSED POSITIVE ION NEGATIVE ION CHEMICAL IONIZATION MASS SPECTROMETRIC APPLICATONS TO ENVIRONMENTAL AND HAZARDOUS WASTE ANALYSIS

    EPA Science Inventory

    The simultaneous acquisition of both positive ion and negative ion data under chemical ionization mass spectrometric conditions can aid in the confirmation of assignments made by electron impact gas chromatography mass spectrometry or electron capture gas chromatography. Pulsed p...

  2. Analysis of pesticide residues by fast gas chromatography in combination with negative chemical ionization mass spectrometry

    Microsoft Academic Search

    Renáta Húšková; Eva Matisová; Svetlana Hrouzková; ?ubomír Švorc

    2009-01-01

    A combination of fast GC with narrow-bore column and bench top quadrupole mass spectrometer (MS) detector in negative chemical ionization (NCI) mode (with methane as reagent gas) is set up and utilized for the ultratrace analysis of 25 selected pesticides. The observed pesticides, belonging to the endocrine disrupting chemicals (EDCs), were from different chemical classes. A comparative study with electron

  3. Optimization of the mass spectrometric analysis of triacylglycerols using negative-ion chemical ionization with ammonia

    Microsoft Academic Search

    Päivi Laakso; Heikki Kallio

    1996-01-01

    Conditions for the mass spectrometric analysis of triacylglycerols,via direct exposure probe, with ammonia negative-ion chemical ionization were optimized. Triacylglycerols were most favorably\\u000a ionized, using the reactant gas pressure of approximately 8500 mtorr at the ion source temperature of 200°C with the instrumentation\\u000a used. Abundant [M-H]? ions were produced under these conditions without the formation of [M+35]? cluster ions, which would

  4. Quantitation of toxaphene in environmental samples using negative ion chemical ionization mass spectrometry

    Microsoft Academic Search

    Deborah L. Swackhamer; M. Judith. Charles; Ronald A. Hites

    1987-01-01

    A method for quantitating toxaphene in environmental samples using methane negative ion chemical ionization (NICI) mass spectrometry in the selected ion mode is given. NICI is highly selective and sensitive for measuring toxaphene. This method monitors ions from each of the homologue groups in the toxaphene mixture having 6 to 10 chlorines corresponding to the M⁻ or the (M -

  5. PENTACHLOROPHENOL IN THE ENVIRONMENT: EVIDENCE FOR ITS ORIGIN FROM COMMERCIAL PENTACHLOROPHENOL BY NEGATIVE CHEMICAL IONIZATION MASS SPECTROMETRY

    EPA Science Inventory

    Commercial pentachlorophenol (PCP) contains significant quantities of tetrachlorophenol (TCP). The occurrence of TCP in environmental samples provides a chemical marker for PCP originating from commercial formulations. Negative chemical ionization mass spectrometry has been used ...

  6. PENTACHLOROPHENOL IN THE ENVIRONMENT. EVIDENCE FOR ITS ORIGIN FROM COMMERCIAL PENTACHLOROPHENOL BY NEGATIVE CHEMICAL IONIZATION MASS SPECTROMETRY

    EPA Science Inventory

    Commercial pentachlorophenol (PCP) contains significant quantities of tetrachlorophenol (TCP). The occurrence of TCP in environmental samples provides a chemical marker for PCP originating from commercial formulations. Negative chemical ionization mass spectrometry has been used ...

  7. Chemical Ionization

    Microsoft Academic Search

    Jürgen H. Gross; Mass Spectrometry

    \\u000a Mass spectrometrists have ever been searching for ionization methods softer than EI, because molecular weight determination\\u000a is key for structure elucidation. Chemical ionization (CI) is the first of the so-called soft ionization methods we are going to discuss (cf. Fig. 1.2).

  8. Detecting benzodiazepines: immunoassays compared with negative chemical ionization gas chromatography/mass spectrometry.

    PubMed

    Fitzgerald, R L; Rexin, D A; Herold, D A

    1994-03-01

    We tested 231 urine samples by six immunoassay methods--EMIT d.a.u., EMIT II, Roche Abuscreen Online, Abbott TDx, Diagnostic Products Corp. (DPC) double-antibody radioimmunoassay (RIA), and Biosite Triage--and by negative chemical ionization gas chromatography/mass spectrometry to determine how the immunoassays performed on samples selected for suspected benzodiazepine use (n = 100) and in random urine drug screening (n = 131). In general, all of the assays were successful in detecting oxazepam and related metabolites, even at concentrations below the stated cutoffs. However, the negative predictive value of benzodiazepine immunoassays for samples selected for suspected benzodiazepine use ranged from 86% to 96%. A primary difference between the test kits was the ability of DPC RIA and Triage to detect lorazepam when other assays did not. Contrary to previous reports, pretreatment of specimens with glucuronidase was not necessary to detect oxazepam-related metabolites with these immunoassays. PMID:8131270

  9. An Ultra-Trace Analysis Technique for SF6 Using Gas Chromatography with Negative Ion Chemical Ionization Mass Spectrometry.

    PubMed

    Jong, Edmund C; Macek, Paul V; Perera, Inoka E; Luxbacher, Kray D; McNair, Harold M

    2015-07-01

    Sulfur hexafluoride (SF6) is widely used as a tracer gas because of its detectability at low concentrations. This attribute of SF6 allows the quantification of both small-scale flows, such as leakage, and large-scale flows, such as atmospheric currents. SF6's high detection sensitivity also facilitates greater usage efficiency and lower operating cost for tracer deployments by reducing quantity requirements. The detectability of SF6 is produced by its high molecular electronegativity. This property provides a high potential for negative ion formation through electron capture thus naturally translating to selective detection using negative ion chemical ionization mass spectrometry (NCI-MS). This paper investigates the potential of using gas chromatography (GC) with NCI-MS for the detection of SF6. The experimental parameters for an ultra-trace SF6 detection method utilizing minimal customizations of the analytical instrument are detailed. A method for the detection of parts per trillion (ppt) level concentrations of SF6 for the purpose of underground ventilation tracer gas analysis was successfully developed in this study. The method utilized a Shimadzu gas chromatography with negative ion chemical ionization mass spectrometry system equipped with an Agilent J&W HP-porous layer open tubular column coated with an alumina oxide (Al2O3) S column. The method detection limit (MDL) analysis as defined by the Environmental Protection Agency of the tracer data showed the method MDL to be 5.2 ppt. PMID:25452581

  10. Fast gas chromatography and negative-ion chemical ionization tandem mass spectrometry for forensic analysis of cannabinoids in whole blood

    Microsoft Academic Search

    Aurélien Thomas; Christèle Widmer; Gérard Hopfgartner; Christian Staub

    2007-01-01

    The present work describes a fast gas chromatography\\/negative-ion chemical ionization tandem mass spectrometric assay (Fast GC\\/NICI-MS\\/MS) for analysis of tetrahydrocannabinol (THC), 11-hydroxy-tetrahydrocannabinol (THC-OH) and 11-nor-9-carboxy-tetrahydrocannabinol (THC-COOH) in whole blood. The cannabinoids were extracted from 500?L of whole blood by a simple liquid–liquid extraction (LLE) and then derivatized by using trifluoroacetic anhydride (TFAA) and hexafluoro-2-propanol (HFIP) as fluorinated agents. Mass spectrometric

  11. Gas chromatography negative ion chemical ionization mass spectrometry: application to the detection of alkyl nitrates and halocarbons in the atmosphere.

    PubMed

    Worton, David R; Mills, Graham P; Oram, David E; Sturges, William T

    2008-08-01

    Alkyl nitrates and very short-lived halocarbon species are important atmospheric trace gas species that are present in the low to sub parts per trillion concentration range. This presents an analytical challenge for their detection and quantification that requires instrumentation with high sensitivity and selectivity. In this paper, we present a new in situ gas chromatograph negative ion chemical ionization mass spectrometer (GC/NICI-MS) coupled to a non-cryogen sample pre-concentration system. This instrument, with detection limits of <0.01 ppt, is capable of detecting and quantifying a large suite of alkyl nitrate and halocarbon species with high sensitivity and precision. The effects of ion source temperature and reagent gas pressure on the ionization efficiency of the NICI mode are investigated and the results are used to optimize the sensitivity. The NICI mode is compared to the more frequently used electron impact (EI) ionization and the enhancements in sensitivity are presented for all the calibrated compounds. PMID:18586255

  12. Fast gas chromatography negative chemical ionization tandem mass spectrometry of explosive compounds using dynamic collision-induced dissociation

    NASA Astrophysics Data System (ADS)

    Collin, Olivier L.; Zimmermann, Carolyn M.; Jackson, Glen P.

    2009-01-01

    The analysis of nine explosive compounds by gas chromatography tandem mass spectrometry (GC-MS/MS) using negative chemical ionization (NCI) was performed under two different conditions: first, a conventional GC separation coupled with a standard ion dissociation method in a quadrupole ion trap (QIT) was performed in segmented selected reaction monitoring mode; second, a fast GC separation on a microbore capillary column was combined with a faster method of collisional activation in ion traps wherein fragmentation is deliberately accomplished during the mass acquisition scan. The conventional GC-MS/MS method provided separation times in 10 min with detection limits between 0.8 and 280 pg on column. The fast GC method with dynamic collision-induced dissociation (DCID) offered a confirmatory method for the analysis of high explosives with separation times under 2.5 min and detection limits between 0.5 and 5 pg on column, without any hardware modifications to the instrument. The implementation of DCID in combination with three-times-faster mass scanning allows the acquisition of tandem mass spectra to at least 5 Hz (while averaging three scans per spectrum). Although detection limits for GC-NCI-MS/MS using conventional CID or DCID are not quite on par with LODs achieved by GC-ECD, the combination of NCI with DCID tandem MS leads to detection limits at least comparable, if not superior, to other mass spectrometric methods. Selected reaction monitoring in the negative ionization mode is anticipated to offer the most selective approach to detecting explosives and eliminating potential interferences, which could ultimately lead to the best detection limits for real, contaminated samples.

  13. QUANTITATION OF MONOSACCHARIDE ISOTOPIC ENRICHMENT IN PHYSIOLOGIC FLUIDS BY ELECTRON IONIZATION OR NEGATIVE CHEMICAL IONIZATION GC/MS USING DI-O-ISOPROPYLIDENE DERIVATIVES.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The aldonitrile pentaacetate and other derivatives lack ions in the electron ionization (EI) spectra possessing an intact hexose structure and thus must be analyzed by chemical ionization GC/MS in order to study multiple isotopomers. We report methods for quantitation of hexose di-O-isopropylidene a...

  14. Identification of acylated xanthone glycosides by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry in positive and negative modes from the lichen Umbilicaria proboscidea.

    PubMed

    Rezanka, Tomás; Dembitsky, Valery M

    2003-05-01

    The xanthoside composition of the crude extract of Umbilicaria proboscidea (L.) Schrader was characterized using LC-UV diode array detection and LC-atmospheric pressure chemical ionization (APCI) MS methods. The presence of acylated xanthone-O-glucosides was determined by both positive and negative ion LC-APCI-MS methods. Based on UV and MS spectral data and NMR spectroscopy, a total of 14 compounds (6-O-acylated umbilicaxanthosides A and B) were identified in U. proboscidea for the first time. In order to further develop the applicability of LC-MS techniques in phytochemical characterization, the effect of different ionization energy on fragmentation was studied using APCI. The optimal ionization conditions were achieved in positive ion APCI by using ammonium acetate buffer and in negative ion APCI by using formic acid (pH 4). PMID:12800927

  15. Quantification of low levels of organochlorine pesticides using small volumes (?100 ?l) of plasma of wild birds through gas chromatography negative chemical ionization mass spectrometry

    Microsoft Academic Search

    Laura B. Rivera-Rodríguez; Ricardo Rodríguez-Estrella; James Jackson Ellington; John J. Evans

    2007-01-01

    A solid phase extraction and gas chromatography with negative chemical ionization mass spectrometry in scan mode (GC-NCI-MS) method was developed to identify and quantify for the first time low levels of organochlorine pesticides (OCs) in plasma samples of less than 100?l from wild birds. The method detection limits ranged from 0.012 to 0.102pg\\/?l and the method reporting limit from 0.036

  16. Identification of acylated xanthone glycosides by liquid chromatography–atmospheric pressure chemical ionization mass spectrometry in positive and negative modes from the lichen Umbilicaria proboscidea

    Microsoft Academic Search

    Tomᚠ?ezanka; Valery M. Dembitsky

    2003-01-01

    The xanthoside composition of the crude extract of Umbilicaria proboscidea (L.) Schrader was characterized using LC–UV diode array detection and LC–atmospheric pressure chemical ionization (APCI) MS methods. The presence of acylated xanthone-O-glucosides was determined by both positive and negative ion LC–APCI-MS methods. Based on UV and MS spectral data and NMR spectroscopy, a total of 14 compounds (6-O-acylated umbilicaxanthosides A

  17. Determination of nitrated polycyclic aromatic hydrocarbons in diesel particulate-related standard reference materials by using gas chromatography\\/mass spectrometry with negative ion chemical ionization

    Microsoft Academic Search

    Dawit Z. Bezabeh; Holly A. Bamford; Michele M. Schantz; Stephen A. Wise

    2003-01-01

    Gas chromatography\\/mass spectrometry (GC\\/MS) with negative ion chemical ionization (NICI) detection was utilized for quantitative determination of nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) in diesel particulate-related standard reference materials (SRMs). Prior to GC\\/MS analysis, isolation of the nitro-PAHs from the complex diesel particulate extract was accomplished using solid phase extraction (SPE) and normal-phase liquid chromatographic (LC) fractionation using an amino\\/cyano stationary

  18. A derivatization assay using gaschromatography/negative chemical ionization tandem mass spectrometry to quantify 3-nitrotyrosine in human plasma.

    PubMed

    Söderling, Ann-Sofi; Ryberg, Henrik; Gabrielsson, Anders; Lärstad, Mona; Torén, Kjell; Niari, Sohbat; Caidahl, Kenneth

    2003-11-01

    Endogenous free or protein-associated 3-nitrotyrosine (3-NT) has been proposed as a biomarker of in vivo oxidative damage caused by nitrating agents. Isotopic dilution assay gaschromatographic/mass spectrometric (GC/MS) techniques have been employed to measure endogenous 3-NT levels. However, the quantitative normal plasma values reported so far are inconsistent. The results vary between the assays; they may have been influenced by in vitro artifactual nitration of tyrosine to 3-NT. In this study, a simple and artifact-free derivatization method for quantifying the endogenous 3-NT content of biological samples by GC/negative chemical ionization MS/MS is presented. The method is based on reduction of the nitro group of the molecule by dithionite, heptafluorobutyric acylation and subsequent methyl derivatization, di-O-methyldi-N-heptafluorobutyryl being the major derivative. The results showed excellent GC and MS properties, such as low background and a favorable fragmentation pattern. Endogenous 3-NT was unequivocally quantified using collision-induced dissociation in the selected reaction monitoring mode, whereas co-elution of unknown compounds interfered in the selected-ion monitoring mode. We found that tyrosine was nitrated in the presence of nitrate anions and heptafluorobutyric anhydride, but the product appeared as a di-O-methylmono-N-heptafluorobutyryl derivative. Therefore, artifactually formed 3-NT did not contribute to the measured endogenous 3-NT level owing to its different derivative structure. The method was applied to determine endogenous 3-NT in human plasma and plasma proteins. A detection limit of 0.03 nM for (13)C(6)-labeled 3-NT in plasma samples was established and the response was linear over a concentration range of 0-50 nM (R(2) > 0.999). The endogenous free 3-NT level (mean +/- SD) in ultrafiltered plasma samples from 12 healthy adults was 0.74 +/- 0.30 nM. The mean concentration of 3-NT in their plasma total proteins was 0.60 +/- 0.40 pmol mg(-1). Hence, the described method is selective, eliminates the problem of artifactual nitration and is feasible for the quantification of free and protein-associated 3-NT in biological samples such as plasma. PMID:14648826

  19. Formation and reactions of negative ions relevant to chemical ionization mass spectrometry. I. Cl mass spectra of organic compounds produced by F? reactions

    PubMed Central

    Tiernan, T. O.; Chang, C.; Cheng, C. C.

    1980-01-01

    A systematic study of the negative-ion chemical ionization mass spectra produced by the reaction of F? with a wide variety of organic compounds has been accomplished. A time-of-flight mass spectrometer fitted with a modified high pressure ion source was employed for these experiments. The F? reagent ion was generated from CF3H or NF3, typically at an ion source pressure of 100 ?m. In pure NF3, F? is the major ion formed and constitutes more than 90% of the total ion intensity. While F? is also the major primary ion formed in pure CF3H, it undergoes rapid ion-molecule reactions at elevated source pressures, yielding (HF)nF? (n = 1?3) ions, which makes CF3H less suitable as a chemical ionization reagent gas. Among the organic compounds investigated were carboxylic acids, ketones, aldehydes, esters, alcohols, phenols, halides, nitriles, nitrobenzene, ethers, amines and hydrocarbons. An intense (M ? 1)? ion was observed in the F? chemical ionization mass spectra of carboxylic acids, ketones, aldehydes and phenols. Alcohols yield only (M + F)? ions upon reaction with F?. A weaker (M + F)? ion was also detected in the F? chemical ionization spectra of carboxylic acids, aldehydes, ketones and nitriles. The F? chemical ionization mass spectra of esters, halides, nitriles, nitrobenzene and ethers are characterized primarily by the ions, RCOO?, X?, CN?, NO2?, and OR?, respectively. In addition, esters show a very weak (M ? 1)? ion (except formates). In the F? chemical ionization spectra of some aliphatic alkanes and o-xylene, a very weak (M + F)? ion was observed. Amines and aliphatic alkenes exhibit only insignificant fragment ions under similar conditions, while aromatic hydrocarbons, such as benzene and toluene are not reactive at all with the F? ion. The mechanisms of the various reactions mentioned are discussed, and several experimental complications are noted. In still other studies, the effects of varying several experimental parameters, including source pressure, relative proportions of the reagent and analyte, and other ion source parameters, on the observed chemical ionization mass spectra were also investigated. In a mixture of NF3 and n-butanol, for example, the ratio of the intensities of the ions characteristic of the alcohol to that of the (HF)nF? ion was found to decrease with increasing sample pressure, with increasing NF3 pressure, and with increasing electron energy. No significant effects on the spectra were observed to result from variation of the source repeller field or the source temperature. The addition of argon to the source as a potential moderator did not alter the F? chemical ionization spectrum significantly, but the use of oxygen appears to inhibit formation of the (HF)nF? cluster ion. The advantages of using F? as a chemical ionization reagent are discussed, and comparisons are made with other reagent ions. PMID:7428746

  20. Negative chemical ionization GC/MS determination of nitrite and nitrate in seawater using exact matching double spike isotope dilution and derivatization with triethyloxonium tetrafluoroborate.

    PubMed

    Pagliano, Enea; Meija, Juris; Sturgeon, Ralph E; Mester, Zoltan; D'Ulivo, Alessandro

    2012-03-01

    The alkylation of nitrite and nitrate by triethyloxonium tetrafluoroborate allows determination of their ethyl esters by headspace gas chromatography/mass spectrometry (GC/MS). In the present study, significant improvement in analytical performance is achieved using negative chemical ionization providing detection limits of 150 ng/L for NO(2)(-) and 600 ng/L for NO(3)(-), an order of magnitude better than those achieved using electron impact ionization. The derivatization procedure was optimized and alkaline conditions adopted to minimize conversion of nitrite to nitrate (determined to be 0.07% at 100 mg/L NO(2)(-)) and to avoid the exchange of oxygen between the analytes and the solvent (water). Quantitation entails use of isotopically enriched standards (N(18)O(2)(-) and (15)NO(3)(-)), which also permits monitoring of potential conversion from nitrite to nitrate during the analysis (double spike isotope dilution). PMID:22320264

  1. Large volume cold on-column injection for gas chromatography-negative chemical ionization-mass spectrometry analysis of selected pesticides in air samples.

    PubMed

    Bailey, Renata; Belzer, Wayne

    2007-02-21

    A new gas chromatographic method is described for the analysis of fungicides captan, captafol, and folpet from organic extracts of air samples using large volume injection (LVI) via a cold on-column (COC) inlet coupled with gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS). Although standard split/splitless injection due to high injection port temperatures (>225 degrees C) have been shown to degrade these thermally labile fungicides, COC injection minimizes degradation. Insecticides such as chlorpyrifos and diazinon were also examined to show added selectivity. By using a solvent vapor exit with the COC inlet, injection volumes of 10-100 microL can be made to lower detection levels. GC-NCI-MS was compared to GC-electron impact ionization-mass spectrometry for each pesticide using LVI-COC injections and was found to be 2-80 times more sensitive, depending on the pesticide. Method detection limit (MDL) values with 100 microL injections were 2.5 microg L-1 for captan, folpet, and diazinon, 5.0 microg L-1 captafol, and 1.0 microg L-1 for chlorpyrifos, with the normal working range examined for sample analysis from MDL to 100 microg L-1. Detection of all pesticides except captafol, used only in the United States but not Canada, was demonstrated from air samples taken from Abbotsford, British Columbia, Canada. PMID:17256963

  2. Determination of microbial fatty acid profiles at femtomolar levels in human urine and the initial marine microfouling community by capillary gas chromatography-chemical ionization mass spectrometry with negative ion detection

    Microsoft Academic Search

    Goran Odham; Anders Tunlid; Gunilla Westerdahl; Lennart Larsson; James B. Guckert; David C. White

    1985-01-01

    Summary Room temperature esterification with the electron capturing pentafluorobenzyl bromide in glass capillaries, with analysis by capillary gas-liquid chromatography coupled with chemical ionization mass spectrometry and negative ion detection in the selected ion mode, allowed detection and identification of fatty acids from micro- bial biofilms at the femtomolar level. This sensitivity was achieved without loss of specificity of the mass

  3. Identification of chlorinated fatty acids in fish by gas chromatography/mass spectrometry with negative ion chemical ionization of pentafluorobenzyl esters.

    PubMed

    Zhuang, Wenshan; McKague, A Bruce; Reeve, Douglas W; Carey, John H

    2004-01-01

    This paper reports the development of a technique for identifying and confirming chlorinated fatty acids previously detected in fish by gas chromatography (GC) with halogen-specific detection (XSD). Fatty acid methyl esters (FAMEs) including chlorinated FAMEs within fractions of reversed-phase high-performance liquid chromatography of transesterified fish extracts were derivatized to pentafluorobenzyl esters, which were subjected to GC/mass spectrometry (MS) with negative ion chemical ionization (NICI). Pentafluorobenzyl esters displayed reasonably good GC characteristics, a very high ionization efficiency and a low degree of fragmentation. Chloride ion chromatograms extracted at m/z 35 and 37 from full scans were utilized for locating traces of chlorinated unknowns in the GC elution profile so that their mass spectra could be readily displayed. Significant ions displayed in the mass spectrum scanned in a narrow range of retention time where a chlorinated unknown was located were evaluated using ion chromatograms extracted at the m/z of these ions. The chromatographic peaks of those ions derived from the analyte were expected to center at that specific retention time, whereas those originating from matrix compounds were not. The isotopic patterns of chlorinated ions were also examined against their theoretical relative abundances. Using this approach, three metabolism-related dichloro fatty acids previously identified by GC/XSD in filet extracts of white sucker sampled downstream from a bleached kraft pulp mill were confirmed: dichlorooctadecanoic, dichlorohexadecanoic and dichlorotetradecanoic acids. In addition, an isomer of dichlorotetradecanoic acid was found in a reference fish sample. As sample preparation is critical in this application, improved conditions for hydrolysis and pentafluorobenzyl esterification are also discussed. PMID:14760613

  4. Measurement of the incorporation and repair of exogenous 5-hydroxymethyl-2'-deoxyuridine in human cells in culture using gas chromatography-negative chemical ionization-mass spectrometry.

    PubMed

    Rogstad, Daniel K; Darwanto, Agus; Herring, Jason L; Rogstad, Katherine Noyes; Burdzy, Artur; Hadley, Scott R; Neidigh, Jonathan W; Sowers, Lawrence C

    2007-12-01

    The DNA of all organisms is constantly damaged by oxidation. Among the array of damage products is 5-hydroxymethyluracil, derived from oxidation of the thymine methyl group. Previous studies have established that HmU can be a sensitive and valuable marker of DNA damage. More recently, the corresponding deoxynucleoside, 5-hydroxymethyl-2'-deoxyuridine (HmdU), has proven to be valuable for the introduction of controlled amounts of a single type of damage lesion into the DNA of replicating cells, which is subsequently repaired by the base excision repair pathway. Complicating the study of HmU formation and repair, however, is the known chemical reactivity of the hydroxymethyl group of HmU under conditions used to hydrolyze DNA. In the work reported here, this chemical property has been exploited by creating conditions that convert HmU to the corresponding methoxymethyluracil (MmU) derivative that can be further derivatized to the 3,5-bis-(trifluoromethyl)benzyl analogue. This derivatized compound can be detected by gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS) with good sensitivity. Using isotopically enriched exogenous HmdU and human osteosarcoma cells (U2OS) in culture, we demonstrate that this method allows for the measurement of HmU in DNA formed from the incorporation of exogenous HmdU. We further demonstrate that the addition of isotopically enriched uridine to the culture medium allows for the simultaneous measurement of DNA replication and repair kinetics. This sensitive and facile method should prove valuable for studies on DNA oxidation damage and repair in living cells. PMID:17914883

  5. 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

    PubMed Central

    Raina, Renata; Hall, Patricia

    2008-01-01

    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 ?L?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 ?L?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 ?L?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 ?L?1) for pesticides with poor NCI response (OPs: sulfotep, phorate, aspon, ethion, and OCs: alachlor, aldrin, perthane, and DDE, DDD, DDT). PMID:19609395

  6. Negative Ion Chemical Ionization Mass Spectrometry for the Analysis of 3,5,6-trichloro-2-pyridinol in Saliva of Rats Exposed to Chlorpyrifos

    SciTech Connect

    Campbell, James A.; Timchalk, Chuck; Kousba, Ahmed A.; Wu, Hong; Valenzuela, Blandina R.; Hoppe, Eric W.

    2005-05-01

    Organophosphorus (OP) insecticides (e.g. chlorpyrifos) are widely used in a variety of applications, and the potential exists for significant occupational and environmental exposures. They have been associated with more occupational poisoning cases than any other class of insecticides. One of the best approaches for accurately assessing human dosimetry and determining risk from both occupational and environmental exposure is biomonitoring. Biological matrices such as blood and urine have been routinely used for biomonitoring; however, other matrices such as saliva represent a simple and readily obtainable fluid. As a result, saliva has been suggested as an alternative biological matrix for the evaluation of a broad range of biomarkers such as environmental contaminants, drugs of abuse, hormones, chemotherapeutics, heavy metals, and pesticides. Chlorpyrifos (CPF), and its major metabolite, 3,5,6-trichloro-2-pyridinol (TCP), have been quantified in urine and blood as a biomarker for exposure to OP insecticides. The purpose of this study was to develop an analytical approach for detecting and quantitating the levels of TCP in saliva obtained from rats exposed to CPF and to evaluate the potential of saliva as a non-invasive biomonitoring matrix. Adult male rats were administered CPF, and blood and saliva were humanely collected for analysis of TCP and CPF. TCP was detected and quantitated in saliva using negative ion chemical ionization mass spectrometry with selected ion monitoring. Initial results indicate that saliva may be potentially utilized as a non-invasive biomonitoring matrix to determine exposure to organophosphate insecticides.

  7. Quantification of low levels of organochlorine pesticides using small volumes (negative chemical ionization mass spectrometry.

    PubMed

    Rivera-Rodríguez, Laura B; Rodríguez-Estrella, Ricardo; Ellington, James Jackson; Evans, John J

    2007-07-01

    A solid phase extraction and gas chromatography with negative chemical ionization mass spectrometry in scan mode (GC-NCI-MS) method was developed to identify and quantify for the first time low levels of organochlorine pesticides (OCs) in plasma samples of less than 100 microl from wild birds. The method detection limits ranged from 0.012 to 0.102 pg/microl and the method reporting limit from 0.036 to 0.307 pg/microl for alpha, gamma, beta and delta-hexachlorocyclohexane (HCH), heptachlor, aldrin, heptachlor epoxide, endosulfan I, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p'-DDE), dieldrin, endrin, endosulfan-II, endrin-aldehyde and endosulfan-sulfate. Pesticide levels in small serum samples from individual Falco sparverius, Sturnella neglecta, Mimus polyglottos and Columbina passerina were quantified. Concentrations ranged from not detected (n/d) to 204.9 pg/microl for some OC pesticides. All levels in the food web in and around cultivated areas showed the presence of pesticides notwithstanding the small areas for agriculture existing in the desert of Baja California peninsula. PMID:17240024

  8. Quantification of L-tryptophan and L-kynurenine by liquid chromatography/electron capture negative ion chemical ionization mass spectrometry.

    PubMed

    Boni, R L; Simpson, J T; Naritsin, D B; Saito, K; Markey, S P

    1994-01-01

    In a number of infectious and inflammatory diseases, stimulation of the immune system can lead to increased accumulation of tryptophan metabolites via induction of kynurenine pathway enzymes in extrahepatic tissues. We developed a liquid chromatographic/mass spectrometric (LC/MS) method suitable for tracing the disposition of 13C isotopomers of L-tryptophan and L-kynurenine in various cultured cell, tissue slice, and whole animal model systems used to investigate tryptophan flux through the kynurenine pathway. The method employs extractive derivatization of the analytes and their 2H internal standards with pentafluorobenzyl bromide in order to enhance the negative ion chemical ionization (NICI) mass spectrometric response. Normal-phase liquid chromatographic separation of derivatized analytes was optimized using a silica column with organic solvents, followed by particle beam transfer and NICI-MS. Standard curves were linear over the range 1-250 ng per sample. Particle beam and mass spectrometric operating parameters were optimized with direct flow injections of 1-(methylamino) anthraquinone, which is an ideal test compound for the evaluation of LC/NICI-MS. The developed method was used to quantify the conversion of (13C6)L-tryptophan to (13C6)L-kynurenine by human monocytes (THP-1) stimulated with interferon-gamma, lung and brain tissue slices obtained from gerbils immune-stimulated with pokeweed mitogen. The effect of whole body immune stimulation on the plasma levels of endogenous L-kynurenine in mice stimulated with interferon-gamma was also quantified. PMID:8155745

  9. Optimization of quadrupole ion storage mass spectrometric conditions for the analysis of selected polybrominated diphenyl ethers. Comparative approach with negative chemical ionization and electron impact mass spectrometry.

    PubMed

    Larrazábal, David; Angeles Martínez, Ma; Eljarrat, Ethel; Barceló, Damiá; Fabrellas, Begoña

    2004-10-01

    Gas chromatography coupled to quadrupole ion storage mass spectrometry (QISTMS) operating in the non-resonant mode is presented as an innovative approach for the analysis of selected polybrominated diphenyl ethers (PBDEs). Although reductions in complexity and time needed for optimization are achieved in comparison with the resonant option, precise adjustment of the mass spectrometric conditions is required. Differences in isolation and fragmentation patterns of target species with degree of bromination were observed. The reliability of the method was confirmed by using standard solutions through the evaluation of certain quality parameters such as accuracy (92-108%), injection repeatability and reproducibility (coefficient of variation below 10% and 15%, respectively). Detection limits ranged from 62 to 621 fg, providing sensitivity similar to that of negative chemical ionisation (NCIMS) and greater than that of electron ionization mass spectrometry. The applicability of QISTMS method to real samples and matrix effects were evaluated through the analysis of some PBDE congeners in a sewage sludge sample from a Spanish waste-water treatment plant. Comparable results were obtained using QISTMS and NCIMS. According to these observations, QISTMS performed in the non-resonant mode may constitute a low-cost, rapid and reliable alternative to high-resolution devices for the analysis of selected PBDEs in environmental samples. PMID:15468104

  10. Development and use of Negative Ion Proton Transfer Reaction Chemical Ionization Mass Spectrometry (NI-PTR-CIMS) for the Measurement of Trace Organic Acids in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Veres, P.; Roberts, J. M.; Warneke, C.; de Gouw, J.; Herndon, S.; Zahniser, M.

    2007-12-01

    Negative-Ion Proton-Transfer Reaction Chemical Ionization Mass Spectrometry (NI-PTR-CIMS) has been developed for real-time measurement of gas-phase organic acids in the atmosphere. The method is based on the non-dissociative proton transfer reactions of CH3COO- with most of the common organic acids. The potential to detect organic acids (monocarboxylic, dicarboxylic, inorganic, and rare acids) has been shown by a number of laboratory investigations. The sensitivity of the instrument to several organic acids has been observed to be on the order of several ion counts per pptv. Detection limits well below the ppbv level are expected for a 1-second integration time. Various instrumental features including zeroing, time response, calibration and validation of the ion chemistry have been investigated and will be discussed. Intercomparison of formic acid measurements with Proton Transfer Reaction Mass Spectrometry (PTR-MS) and Quantum Cascade Laser IR absorption (QCL) serve to validate this measurement technique. Further development of this instrument will provide a fast, sensitive, and selective measurement technique for gas-phase acids. NI-PTR-CIMS has great potential for use in atmospheric chemistry field studies.

  11. Artifact-free quantification of free 3-chlorotyrosine, 3-bromotyrosine, and 3-nitrotyrosine in human plasma by electron capture-negative chemical ionization gas chromatography mass spectrometry and liquid chromatography-electrospray ionization tandem mass spectrometry.

    PubMed

    Gaut, Joseph P; Byun, Jaeman; Tran, Hung D; Heinecke, Jay W

    2002-01-15

    Halogenation and nitration of biomolecules have been proposed as key mechanisms of host defense against bacteria, fungi, and viruses. Reactive oxidants also have the potential to damage host tissue, and they have been implicated in disease. In the current studies, we describe specific, sensitive, and quantitative methods for detecting three stable markers of oxidative damage: 3-chlorotyrosine, 3-bromotyrosine, and 3-nitrotyrosine. Our results indicate that electron capture-negative chemical ionization-gas chromatography/mass spectrometry (EC-NCI GC/MS) is 100-fold more sensitive than liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-MS/MS) for analyzing authentic 3-chlorotyrosine, 3-bromotyrosine, and 3-nitrotyrosine. Using an isotopomer of tyrosine to evaluate artifactual production of the analytes during sample preparation and analysis, we found that artifact generation was negligible with either technique. However, LC-MS/MS proved cumbersome for analyzing multiple samples because it required 1.5 h of run and equilibration time per analysis. In contrast, EC-NCI GC/MS required only 5 min of run time per analysis. Using EC-NCI GC/MS, we were able to detect and quantify attomole levels of free 3-chlorotyrosine, 3-bromotyrosine, and 3-nitrotyrosine in human plasma. Our results indicate that EC-NCI GC/MS is a sensitive and specific method for quantifying free 3-chlorotyrosine, 3-bromotyrosine, and 3-nitrotyrosine in biological fluids in a single, rapid analysis and that it avoids generating any of the analytes ex vivo. PMID:11779118

  12. Development and validation of a gas chromatography–negative chemical ionization tandem mass spectrometry method for the determination of ethyl glucuronide in hair and its application to forensic toxicology

    Microsoft Academic Search

    Hicham Kharbouche; Frank Sporkert; Stéphanie Troxler; Marc Augsburger; Patrice Mangin; Christian Staub

    2009-01-01

    Ethyl glucuronide (EtG) is a minor and direct metabolite of ethanol. EtG is incorporated into the growing hair allowing retrospective investigation of chronic alcohol abuse. In this study, we report the development and the validation of a method using gas chromatography–negative chemical ionization tandem mass spectrometry (GC–NCI-MS\\/MS) for the quantification of EtG in hair. EtG was extracted from about 30mg

  13. Analysis of low erucic acid turnip rapeseed oil ( Brassica campestris ) by negative ion chemical ionization tandem mass spectrometry. A method giving information on the fatty acid composition in positions sn -2 and sn -1\\/3 of triacylglycerols

    Microsoft Academic Search

    Heikki Kallio; Graeme Currie

    1993-01-01

    A tandem mass spectrometric method is described for the rapid analysis of fatty acid combinations in mixtures of triacylglycerols.\\u000a Triacylglycerols were introduced into a triple quadrupole mass spectrometervia a direct exposure probe and deprotonated using ammonia negative ion chemical ionization. Collisionally activated spectra\\u000a were obtained and the resulting fragments used to identify the fatty acid constituents, and the fatty acids

  14. Chemical protection against ionizing radiation

    NASA Astrophysics Data System (ADS)

    Maisin, J. R.

    Some of the problems related to chemical protection against ionizing radiation are discussed with emphasis on : definition, classification, degree of protection, mechanisms of action and toxicity. Results on the biological response modifyers (BRMs) and on the combination of nontoxic (i.e. low) doses of sulphydryl radioprotectors and BRMs are presented.

  15. Flow reactor and triple quadrupole mass spectrometer investigations of negative ion reactions involving nitric acid: Implications for atmospheric HNO3 detection by chemical ionization mass spectrometry

    Microsoft Academic Search

    O. Moehler; F. Arnold

    1991-01-01

    Atmospheric nitric acid measurements by ACIMS (Active Chemical Ionization Mass Spectrometry) are based on ion-molecule reactions of CO3-(H2O)n and NO3-(H2O)n with HNO3. We have studied these reactions in the laboratory using a flow tube apparatus with mass spectrometric detection of reactant and product ions. Both product ion distributions and rate coefficients were measured. All reactions were investigated in an N2-buffer

  16. Determination of naltrexone and 6-beta-naltrexol in plasma by solid-phase extraction and gas chromatography-negative ion chemical ionization-mass spectrometry.

    PubMed

    Huang, W; Moody, D E; Foltz, R L; Walsh, S L

    1997-01-01

    Solid-phase extraction (SPE) and a one-step derivatization are combined with gas chromatography-negative ion chemical ionization-mass spectrometry to simplify a previously reported method for the determination of naltrexone and its metabolite, 6-beta-naltrexol, in human plasma. Deuterated isotopomers of naltrexone and 6-beta-naltrexol are used as internal standards. After SPE, the extracts are derivatized with pentafluoropropionic anhydride at room temperature to form predominantly the bispentafluoropropionyl derivative of naltrexone and the trispentafluoropropionyl derivative of 6-beta-naltrexol. The derivatized extracts are analyzed by monitoring ion currents at m/z 633 (naltrexone), m/z 636 (naltrexone-2H3), m/z 633 6-beta-naltrexol), and m/z 640 (6-beta-naltrexol-2H7). Control plasma samples containing 0.3, 3, or 30 ng/nl of each analyte were analyzed for precision and accuracy with the following results: intra-assay, the percentage of target concentrations were 107-113% for naltrexone and 107-120% for 6-beta-naltrexol, and the coefficients of variation (CVs) were 3.1-6.3% for naltrexone and 3.1-5.7% for 6-beta-naltrexol; interassay, the percentage of target concentrations were 103-110% for naltrexone and 110-113% for 6-beta-naltrexol, and the CVs were 6.1-9.1% for naltrexone and 5.9-9.1% for 6-beta-naltrexol. At the limit of quantitation (LOQ) of 0.1 ng/ml, both analytes quantified within 20% of the target concentration with CVs less than 17%. The extraction recoveries determined at 0.3 and 30 ng/ml were 79 and 80% for naltrexone and 76 and 75% for 6-beta-naltrexol. Bench-top stability tested with concentrations of 0.3 and 3.0 ng/ml did not decrease more than 10% from the zero-hour controls at 3, 6 and 24 h. Selectively was determined using plasma from six donors and none showed interfering peaks greater than 22% of the LOQ for naltrexone and 53% of the LOQ for 6-beta-naltrexol. Using this method, naltrexone and 6-beta-naltrexol were readily detected in plasma specimens collected 5.5 h after oral doses of 25 or 100 mg naltrexone. Following discontinuation of treatment, naltrexone was detected 30 h after the 100-mg dose, whereas 6-beta-naltrexol was detected 125 h after both the 25- and 100-mg doses. PMID:9248940

  17. Measurement of HONO, HNCO, and other inorganic acids by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS): application to biomass burning emissions

    NASA Astrophysics Data System (ADS)

    Roberts, J. M.; Veres, P.; Warneke, C.; Neuman, J. A.; Washenfelder, R. A.; Brown, S. S.; Baasandorj, M.; Burkholder, J. B.; Burling, I. R.; Johnson, T. J.; Yokelson, R. J.; de Gouw, J.

    2010-07-01

    A negative-ion proton-transfer chemical ionization mass spectrometric technique (NI-PT-CIMS), using acetate as the reagent ion, was applied to the measurement of volatile inorganic acids of atmospheric interest: hydrochloric (HCl), nitrous (HONO), nitric (HNO3), and isocyanic (HNCO) acids. Gas phase calibrations through the sampling inlet showed the method to be intrinsically sensitive (6-16 cts/pptv), but prone to inlet effects for HNO3 and HCl. The ion chemistry was found to be insensitive to water vapor concentrations, in agreement with previous studies of carboxylic acids. The inlet equilibration times for HNCO and HONO were 2 to 4 s, allowing for measurement in biomass burning studies. Several potential interferences in HONO measurements were examined: decomposition of HNO3·NO3- clusters within the CIMS, and NO2-water production on inlet surfaces, and were quite minor (?1%, 3.3%, respectively). The detection limits of the method were limited by the instrument backgrounds in the ion source and flow tube, and were estimated to range between 16 and 50 pptv (parts per trillion by volume) for a 1 min average. The comparison of HONO measured by CIMS and by in situ FTIR showed good correlation and agreement to within 17%. The method provided rapid and accurate measurements of HNCO and HONO in controlled biomass burning studies, in which both acids were seen to be important products.

  18. Measurement of HONO, HNCO, and other inorganic acids by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS): application to biomass burning emissions

    NASA Astrophysics Data System (ADS)

    Roberts, J. M.; Veres, P.; Warneke, C.; Neuman, J. A.; Washenfelder, R. A.; Brown, S. S.; Baasandorj, M.; Burkholder, J. B.; Burling, I. R.; Johnson, T. J.; Yokelson, R. J.; de Gouw, J.

    2010-01-01

    A negative-ion proton transfer chemical ionization mass spectrometric technique (NI-PT-CIMS), using acetate as the reagent ion, was applied to the measurement of volatile inorganic acids of atmospheric interest: hydrochloric (HCl), nitrous (HONO), nitric (HNO3), and isocyanic (HNCO) acids. Gas phase calibrations through the sampling inlet showed the method to be intrinsically sensitive (6-16 cts/pptv), but prone to inlet effects for HNO3 and HCl. The ion chemistry was found to be insensitive to water vapor concentrations, in agreement with previous studies of carboxylic acids. The inlet equilibration times for HNCO and HONO were 2 to 4 s, allowing for measurement in biomass burning studies. Several potential interferences in HONO measurements were examined: decomposition of HNO3·NO3- clusters within the CIMS, and NO2-water production on inlet surfaces, and were quite minor (?1%, 3.3%, respectively). The detection limits of the method were limited by the instrument backgrounds in the ion source and flow tube, and were estimated to range between 16 and 50 pptv (parts per trillion by volume) for a 1 min average. The comparison of HONO measured by CIMS and by in situ FTIR showed good correlation and agreement to within 17%. The method provided rapid and accurate measurements of HNCO and HONO in controlled biomass burning studies, in which both acids were seen to be important products.

  19. Determination of 2-, 3-, 4-methylpentanoic and cyclohexanecarboxylic acids in wine: development of a selective method based on solid phase extraction and gas chromatography-negative chemical ionization mass spectrometry and its application to different wines and alcoholic beverages.

    PubMed

    Gracia-Moreno, Elisa; Lopez, Ricardo; Ferreira, Vicente

    2015-02-13

    A method to analyse 2-methylpentanoic, 3-methylpentanoic and 4-methylpentanoic acids as well as cyclohexanecarboxylic acid has been developed and applied to wine and other alcoholic beverages. Selective isolation with solid phase extraction, derivatization with 2,3,4,5,6-pentafluorobenzyl bromide at room temperature for 30 minutes, and further analysis by gas chromatography-mass spectrometry in negative chemical ionization mode provides detection limits between 0.4 and 2.4 ng/L. Good linearity up to 3.6 ?g/L, satisfactory reproducibility (RSD<10%) and signal recovery of around 100% represent a robust method of analysis. Concentration data of these analytes in wine and other alcoholic beverages are reported for the first time. The levels found ranged from the method detection limits to 2630 ng/L, 2040 ng/L and 3810 ng/L for 2-, 3- and 4-methylpentanoic acids, respectively, and to 1780 ng/L for cyclohexanecarboxylic acid. There are significant differences depending on the type of wine or beverage. Distilled beverages, beer and aged wines have higher contents in methylpentanoic and cyclohexanecarboxylic acids. PMID:25601317

  20. Production of negative osmium ions by laser desorption and ionization.

    PubMed

    Rodríguez, D; Sonnenschein, V; Blaum, K; Block, M; Kluge, H-J; Lallena, A M; Raeder, S; Wendt, K

    2010-01-01

    The interest to produce negative osmium ions is manifold in the realm of high-accuracy ion trap experiments: high-resolution nearly Doppler-free laser spectroscopy, antihydrogen formation in its ground state, and contributions to neutrino mass spectrometry. Production of these ions is generally accomplished by sputtering an Os sample with Cs(+) ions at tens of keV. Though this is a well-established method commonly used at accelerators, these kind of sources are quite demanding and tricky to operate. Therefore, the development of a more straightforward and cost effective production scheme will be of benefit for ion trap and other experiments. Such a scheme makes use of desorption and ionization with pulsed lasers and identification of the ions by time-of-flight mass spectrometry. First investigations of negative osmium ion production using a pulsed laser for desorption and ionization and a commercial matrix-assisted laser desorption/ionization time-of-flight system for identification has demonstrated the suitability of this technique. More than 10(3) negative osmium ions per shot were registered after bombarding pure osmium powder with a 5 ns pulse width Nd:yttrium aluminum garnet laser. The limitation in the ion number was imposed by the detection limit of the microchannel plate detector. PMID:20113087

  1. Production of negative osmium ions by laser desorption and ionization

    NASA Astrophysics Data System (ADS)

    Rodríguez, D.; Sonnenschein, V.; Blaum, K.; Block, M.; Kluge, H.-J.; Lallena, A. M.; Raeder, S.; Wendt, K.

    2010-01-01

    The interest to produce negative osmium ions is manifold in the realm of high-accuracy ion trap experiments: high-resolution nearly Doppler-free laser spectroscopy, antihydrogen formation in its ground state, and contributions to neutrino mass spectrometry. Production of these ions is generally accomplished by sputtering an Os sample with Cs+ ions at tens of keV. Though this is a well-established method commonly used at accelerators, these kind of sources are quite demanding and tricky to operate. Therefore, the development of a more straightforward and cost effective production scheme will be of benefit for ion trap and other experiments. Such a scheme makes use of desorption and ionization with pulsed lasers and identification of the ions by time-of-flight mass spectrometry. First investigations of negative osmium ion production using a pulsed laser for desorption and ionization and a commercial matrix-assisted laser desorption/ionization time-of-flight system for identification has demonstrated the suitability of this technique. More than 103 negative osmium ions per shot were registered after bombarding pure osmium powder with a 5 ns pulse width Nd:yttrium aluminum garnet laser. The limitation in the ion number was imposed by the detection limit of the microchannel plate detector.

  2. Unresolved issues in the analysis of F2-isoprostanes, F4-neuroprostanes, isofurans, neurofurans, and F2-dihomo-isoprostanes in body fluids and tissue using gas chromatography/negative-ion chemical-ionization mass spectrometry.

    PubMed

    Yen, H-C; Wei, H-J; Lin, C-L

    2015-07-01

    F2-isoprostanes (F2-IsoPs) generated from arachidonic acid (AA) have been recognized as the most reliable marker of nonenzymatic lipid peroxidation in vivo. F2-IsoPs are initially produced in esterified form on phospholipids, and then released into body fluids in free form. The same mechanism can lead to generation of F4-neuroprostanes (F4-NPs) and F2-dihomo-IsoPs from docosahexaenoic acid (DHA) and adrenic acid, respectively. In addition, isofurans (IsoFs) and neurofurans (NFs) may be preferentially produced from AA and DHA, respectively, under high oxygen tension. The detection of F2-IsoPs using gas chromatography/negative-ion chemical-ionization mass spectrometry (GC/NICI-MS) has been widely employed, which is important for human body fluids containing low quantity of free-form F2-IsoPs. F4-NPs have also been detected using GC/NICI-MS, but multiple peaks need to be quantified. In this paper, we summarize the basic workflow of the GC/NICI-MS method for analyzing F2-IsoPs and F4-NPs, and various formats of assays conducted by different groups. We then discuss the feasibility of simultaneous analysis of IsoFs, NFs, and F2-dihomo-IsoPs with F2-IsoPs or F4-NPs. Representative GC chromatograms for analyzing these markers in human body fluids and rat brain tissue are demonstrated. Furthermore, we discuss several factors that may affect the performance of the analysis, such as those related to the sample processing steps, interference from specimens, types of GC liners used, and the addition of electron multiplier voltage in the method setting for the MS detector. Finally, we question the appropriateness of measuring total (free plus esterified) levels of these markers in body fluids. PMID:25812589

  3. ELECTRON-CAPTURE NEGATIVE IONIZATION CALIBRANTS FOR MAGNETIC SECTOR MASS SPECTROMETERS

    EPA Science Inventory

    Fomblin poly(perfluoropropylene oxide). FK (perfluorokerosene) and FC-43 (perflurotributylamine) are investigated as mass calibrants in electron-capture negative ionization mass spectrometry on a magnetic sector hybrid mass spectrometer. This work provides exact negative ion mass...

  4. Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides

    USGS Publications Warehouse

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

    2001-01-01

    An evaluation of over 75 pesticides by high-performance liquid chromatography/mass spectrometry (HPLC/MS) clearly shows that different classes of pesticides are more sensitive using either atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI). For example, neutral and basic pesticides (phenylureas, triazines) are more sensitive using APCI (especially positive ion). While cationic and anionic herbicides (bipyridylium ions, sulfonic acids) are more sensitive using ESI (especially negative ion). These data are expressed graphically in a figure called an ionization-continuum diagram, which shows that protonation in the gas phase (proton affinity) and polarity in solution, expressed as proton addition or subtraction (pKa), is useful in selecting APCI or ESI. Furthermore, sodium adduct formation commonly occurs using positive ion ESI but not using positive ion APCI, which reflects the different mechanisms of ionization and strengthens the usefulness of the ionization-continuum diagram. The data also show that the concept of "wrong-way around" ESI (the sensitivity of acidic pesticides in an acidic mobile phase) is a useful modification of simple pKa theory for mobile-phase selection. Finally, this finding is used to enhance the chromatographic separation of oxanilic and sulfonic acid herbicides while maintaining good sensitivity in LC/MS using ESI negative.

  5. Tetramethylammonium hydroxide as a reagent for complex mixture analysis by negative ion electrospray ionization mass spectrometry.

    PubMed

    Lobodin, Vladislav V; Juyal, Priyanka; McKenna, Amy M; Rodgers, Ryan P; Marshall, Alan G

    2013-08-20

    Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) enables the direct characterization of complex mixtures without prior fractionation. High mass resolution can distinguish peaks separated by as little as 1.1 mDa), and high mass accuracy enables assignment of elemental compositions in mixtures that contain tens of thousands of individual components (crude oil). Negative electrospray ionization (ESI) is particularly useful for the speciation of the most acidic petroleum components that are implicated in oil production and processing problems. Here, we replace conventional ammonium hydroxide by tetramethylammonium hydroxide (TMAH, a much stronger base, with higher solubility in toluene) to more uniformly deprotonate acidic components of complex mixtures by negative ESI FTICR MS. The detailed compositional analysis of four crude oils (light to heavy, from different geographical locations) reveals that TMAH reagent accesses 1.5-6 times as many elemental compositions, spanning a much wider range of chemical classes than does NH4OH. For example, TMAH reagent produces abundant negative electrosprayed ions from less acidic and neutral species that are in low abundance or absent with NH4OH reagent. More importantly, the increased compositional coverage of TMAH-modified solvent systems maintains, or even surpasses, the compositional information for the most acidic species. The method is not limited to petroleum-derived materials and could be applied to the analysis of dissolved organic matter, coal, lipids, and other naturally occurring compositionally complex organic mixtures. PMID:23919350

  6. Nanoparticle Synthesis by Ionizing Source Gas in Chemical Vapor Deposition

    Microsoft Academic Search

    Motoaki Adachi; Shigeki Tsukui; Kikuo Okuyama

    2003-01-01

    A new chemical vapor deposition (CVD) method called ionization CVD, in which reactant gases are ionized, was developed for the synthesis of nanoparticles. In such a CVD method, the particles formed are charged and the repulsive Coulombic force between them suppresses their coagulation, producing non-agglomerated particles that have a relatively high number concentration and small size. A tetraethylorthosilicate (TEOS)\\/O2 mixture

  7. Effect of sample compositions on chemical analysis using matrix-assisted laser desorption ionization mass spectrometry

    SciTech Connect

    Schriemer, D.; Dai, Y.; Li, L. [Univ. of Alberta, Edmonton, Alberta (Canada). Dept. of Chemistry

    1996-12-31

    Matrix-assisted laser desorption ionization (MALDI) is an effective ionization technique for mass spectrometry. It takes advantages of some unique properties of certain organic chemicals to provide entrapment, isolation, vaporization, and ionization of the analyte of interest. While the main application of the MALDI technique is currently in the area of biological molecule analysis, it is possible to use this technique for monitoring polymer chemistry such as degradation processes. This is potentially important for studying and developing environmentally degradable polymers. Direct analysis of the analyte in real-world samples is possible with MALDI. However, there is a significant effect of the overall composition of a sample on the detectability and performance of MALDI. Two examples are given to illustrate the positive and negative effects of buffers, salts, and additives on the MALDI sample preparation.

  8. An atmospheric pressure chemical ionization study of the positive and negative ion chemistry of the hydrofluorocarbons 1,1-difluoroethane (HFC-152a) and 1,1,1,2-tetrafluoroethane (HFC-134a) and of perfluoro-n-hexane (FC-72) in air plasma at atmospheric pressure.

    PubMed

    Marotta, Ester; Paradisi, Cristina; Scorrano, Gianfranco

    2004-07-01

    A report is given on the ionization/dissociation behavior of the title compounds within air plasmas produced by electrical corona discharges at atmospheric pressure: both positive and negative ions were investigated at different temperatures using atmospheric pressure chemical ionization mass spectrometry (APCI-MS). CHF(2)CH(3) (HFC-152a) undergoes efficient ionic oxidation to C(2)H(5)O(+), in which the oxygen comes from water present in the plasma. In contrast, CF(3)CH(2)F (HFC-134a) does not produce any characteristic positive ion under APCI conditions, its presence within the plasma being revealed only as a neutral ligand in ion-molecule complexes with ions of the background (H(3)O(+) and NO(+)). Analogously, the perfluorocarbon FC-72 (n-C(6)F(14)) does not produce significant positive ions at 30 degrees C: at high temperature, however, it undergoes dissociative ionization to form many product ions including C(3)F(6)(+), C(2)F(4)(+), C(n)F(2n+1)(+) and a few families of oxygen containing cations (C(n)F(2n+1)OH(2)(+), C(n)F(2n)OH(+), C(n)F(2n-1)O(+), C(n)F(2n-1)O(2)H(2)(+), C(n)F(2n-2)O(2)H(+)) which are suggested to derive from C(n)F(2n+1)(+) in a cascade of steps initiated by condensation with water followed by steps of HF elimination and H(2)O addition. Negative ions formed from the fluoroethanes CHF(2)CH(3) and CF(3)CH(2)F (M) include complexes with ions of the background, O(2)(-)(M), O(3)(-)(M) and some higher complexes involving also water, and complexes of the fluoride ion, F(-)(H(2)O), F(-)(M) and higher complexes with both M and H(2)O also together. The interesting product O(2)(-)(HF) is also formed from 1,1-difluoroethane. In contrast to the HFCs, perfluoro-n-hexane gives stable molecular anions, M(-), which at low source temperature or in humidified air are also detected as hydrates, M(-)(H(2)O). In addition, in humidified air F(-)(H(2)O)(n) complexes are also formed. The reactions leading to all major positive and negative product ions are discussed also with reference to available thermochemical data and relevant literature reports. The effects on both positive and negative APCI spectra due to ion activation via increasing V(cone) are also reported and discussed: several interesting endothermic processes are observed under these conditions. The results provide important information on the role of ionic reactions in non-thermal plasma processes. PMID:15282758

  9. Collision-Based Ionization: Bridging the Gap between Chemical Ionization and Aerosol Particle Diffusion Charging

    Microsoft Academic Search

    Vinay Premnath; Derek Oberreit; Christopher J. Hogan Jr

    2011-01-01

    In diffusion charging theory, it is assumed that each ion–particle collision leads to the transfer of charge from ion to particle, and that charge transfer will not occur upon collision between a vapor molecule and a charged particle. However, in chemical ionization, charge transfer can occur in two directions—from charge-donating ion to vapor molecule and back from charged vapor molecule

  10. Characterization of Nonpolar Lipids and Selected Steroids by Using Laser-Induced Acoustic Desorption/Chemical Ionization, Atmospheric Pressure Chemical Ionization, and Electrospray Ionization Mass Spectrometry†

    PubMed Central

    Jin, Zhicheng; Daiya, Shivani; Kenttämaa, Hilkka I.

    2011-01-01

    Laser-induced acoustic desorption (LIAD) combined with ClMn(H2O)+ chemical ionization (CI) was tested for the analysis of nonpolar lipids and selected steroids in a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). The nonpolar lipids studied, cholesterol, 5?-cholestane, cholesta-3,5-diene, squalene, and ?-carotene, were found to solely form the desired water replacement product (adduct-H2O) with the ClMn(H2O)+ ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H2O ions, but less abundant adduct-2H2O ions were also observed. Neither (+)APCI nor (+)ESI can ionize the saturated hydrocarbon lipid, cholestane. APCI successfully ionizes the unsaturated hydrocarbon lipids to form exclusively the intact protonated analytes. However, it causes extensive fragmentation for cholesterol and the steroids. The worst case is cholesterol that does not produce any stable protonated molecules. On the other hand, ESI cannot ionize any of the hydrocarbon analytes, saturated or unsaturated. However, ESI can be used to protonate the oxygen-containing analytes with substantially less fragmentation than for APCI in all cases except for cholesterol and estrone. In conclusion, LIAD/ClMn(H2O)+ chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids. PMID:21528012

  11. Characterization of nonpolar lipids and steroids by using laser-induced acoustic desorption/chemical ionization, atmospheric pressure chemical ionization, and electrospray ionization mass spectrometry

    SciTech Connect

    Jin, Z.; Daiya, S.; Kenttämaa, Hilkka I.

    2011-01-01

    Laser-induced acoustic desorption (LIAD) combined with ClMn(H{sub 2}O){sup +} chemical ionization (CI) was tested for the analysis of nonpolar lipids and selected steroids in a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). The nonpolar lipids studied, cholesterol, 5?-cholestane, cholesta-3,5-diene, squalene, and ?-carotene, were found to solely form the desired water replacement product (adduct-H{sub 2}O) upon reaction with the ClMn(H{sub 2}O){sup +} ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H{sub 2}O ions, but less abundant adduct-2H{sub 2}O ions were also observed. Neither (+)APCI nor (+)ESI can ionize the saturated hydrocarbon lipid, cholestane. APCI successfully ionizes the unsaturated hydrocarbon lipids to form exclusively the intact protonated analytes. However, it causes extensive fragmentation for cholesterol and the steroids. The worst case is cholesterol that does not produce any stable protonated molecules. On the other hand, ESI cannot ionize any of the hydrocarbon analytes, saturated or unsaturated. However, ESI can be used to protonate the oxygen-containing analytes with substantially less fragmentation than for APCI in all cases except for cholesterol and estrone. In conclusion, LIAD/ClMn(H{sub 2}O){sup +} chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids.

  12. The influence of negative ionization of the air on motor activity in Syrian hamsters ( Masocricetus auratus Waterhouse) in light conditions

    NASA Astrophysics Data System (ADS)

    Lenkiewicz, Zofia; Dabrowska, Barbara; Schiffer, Zofia

    1989-12-01

    The motor activity of Syrian hamsters ( Mesocricetus auratus Waterhouse) under the influence of negative ionization of the atmosphere applied for 10, 20 or 30 min per day was investigated. An ionizer with output of 14000 light negative ions per 1 cm3 of air was used. Studies carried out in the light phase of a 12?12 h light/dark regime revealed a relation between the reaction of the animal and the time of day at which ionization was applied. Ionization for 20 or 30 min in the light phase decreased motor activity, while 10 min of ionization increased it compared to control animals. Ionization in the dark phase gave a more distinct rise in activity than that applied in the light phase for all three durations of ionization.

  13. Rapid differentiation of refined fuels using negative electrospray ionization/mass spectrometry

    USGS Publications Warehouse

    Rostad, C.E.; Hostettler, F.D.

    2005-01-01

    Negative electrospray ionization/MS enabled rapid, specific, and selective screening for unique polar components at parts per million concentrations in commercial hydrocarbon products without extensive sample preparation, separation, chromatography, or quantitation. Commercial fuel types were analyzed with this method, including kerosene, jet fuel, white gas, charcoal lighter fluid, on-road and off-road diesel fuels, and various grades and brands of gasolines. The different types of fuels produced unique and relatively simple spectra. These analyses were then applied to hydrocarbon samples from a large, long-term fuel spill. Although the alkane, isoprenoid, and alkylcyclohexane portions began to biodegrade or weather, the polar components in these samples remained relatively unchanged. The type of fuel involved was readily identified by negative electrospray ionization/MS. This is an abstract of a paper presented at the 230th ACS National Meeting (Washington, DC 8/28/2005-9/1/2005).

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

    SciTech Connect

    Alton, G.D. [Oak Ridge National Lab., TN (United States); Welton, R.F. [Oak Ridge Institute of Science and Engineering, TN (United States); Cui, B. [China Institute of Atomic Energy, Beijing (China)] [and others

    1996-12-31

    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{sup +} estimated to exceed 60% and as high as {approximately}50% for F{sup -} generation. The design features, operational principles, and initial performance of the source for generating Cs{sup +} and F{sup -}, when operated with Cs, are discussed in this article.

  15. A Thermal Desorption Chemical Ionization Ion Trap Mass Spectrometer for the Chemical Characterization of Ultrafine Aerosol Particles

    Microsoft Academic Search

    Andreas Held; G. Jeffrey Rathbone; James N. Smith

    2009-01-01

    The development of a thermal desorption chemical ionization ion trap mass spectrometer for the chemical characterization of ultrafine aerosol particles is reported and first experimental results are presented. Atmospheric particles are size-classified and collected using a unipolar charger, a radial differential mobility analyzer and an electrostatic precipitator, and analyzed after thermal desorption and chemical ionization using an ion trap mass

  16. A Negative-Surface Ionization for Generation of Halogen Radioactive Ion Beams

    SciTech Connect

    Zaim, H.

    2001-04-16

    A simple and efficient negative surface ionization source has been designed, fabricated and initially tested for on-line generation of radioactive ion beams of the halogens (Cl, Br, I, and At) for use in the nuclear-structure and nuclear-astrophysics research programs at the Holifield Radioactive Ion Beam Facility. The source utilizes a solid, spherical geometry LaB{sub 6} surface ionizer for forming highly electronegative atoms and molecules. Despite its widely publicized propensity for being easily poisoned, no evidences of this effect were experienced during testing of the source. Nominal efficiencies of 15% for Br{sup {minus}} beam generation were obtained during off-line evaluation of the source with AlBr3 feed material when account is taken of the fractional dissociation of the molecule. Principles of operation, design features, operational parameter data, initial performance results, and beam quality data (emittance) are presented in this article.

  17. Identification of phosphorylation sites in phosphopeptides by positive and negative mode electrospray ionization-tandem mass spectrometry

    Microsoft Academic Search

    Mark Busman; Kevin L. Schey; John E. Oatis; Daniel R. Knapp

    1996-01-01

    A series of synthetic mono- and diphosphorylated peptides has been analyzed by positive and negative mode electrospray ionization-tandem\\u000a mass spectrometry. The synthetic peptides are serine- and threonine-phosphorylated analogs of proteolytic fragments from the\\u000a C-terminal region of rhodopsin. Use of positive and negative modes of electrospray ionization to produce ions for tandem mass\\u000a spectrometry via low energy collision-induced dissociation was explored.

  18. Characterization of astaxanthin esters in Haematococcus pluvialis by liquid chromatography–atmospheric pressure chemical ionization mass spectrometry

    Microsoft Academic Search

    Fengping Miao; Dayan Lu; Yeguang Li; Mingtao Zeng

    2006-01-01

    After first being analyzed by HPLC, 4 free carotenoids, 15 astaxanthin monoesters, 12 astaxanthin diesters, and 3 astacin monoesters in Haematococcus pluvialis were identified by liquid chromatography–atmospheric pressure chemical ionization mass spectrometry (LC–(APCI)MS). Identification of each compound was based on the characteristic fragment ions of the positive ion mode, negative ion mode, and MS2. Astaxanthin esters were identified based on

  19. Rapid differentiation of refined fuels using negative electrospray ionization/mass spectrometry

    USGS Publications Warehouse

    Rostad, C.E.; Hostettler, F.D.

    2005-01-01

    An application of electrospray ionization/mass spectrometry for identification of various commercially refined fuels using the unique signature of polar components, was investigated. The samples were analyzed by mass spectrometry using negative electrospray on an Agilent Series 1100 liquid chromatograph/mass spectrometer. These analysis were applied to hydrocarbon samples from a large, long-term fuel spill which were taken from the subsurface and different extent of biodegradation or weathering. The technique provided rapid identification of hydrocarbons released into the environment because these polar compounds are unique in different fuels.

  20. Microchip atmospheric pressure chemical ionization source for mass spectrometry.

    PubMed

    Ostman, Pekka; Marttila, Seppo J; Kotiaho, Tapio; Franssila, Sami; Kostiainen, Risto

    2004-11-15

    A novel microchip heated nebulizer for atmospheric pressure chemical ionization mass spectrometry is presented. Anisotropic wet etching is used to fabricate the flow channels, inlet, and nozzle on a silicon wafer. An integrated heater of aluminum is sputtered on a glass wafer. The two wafers are jointed by anodic bonding, creating a two-dimensional version of an APCI source with a sample channel in the middle and gas channels symmetrically on both sides. The ionization is initiated with an external corona-discharge needle positioned 2 mm in front of the microchip heated nebulizer. The microchip APCI source provides flow rates down to 50 nL/min, stable long-term analysis with chip lifetime of weeks, good quantitative repeatability (RSD < 10%) and linearity (r(2) > 0.995) with linear dynamic rage of at least 4 orders of magnitude, and cost-efficient manufacturing. The limit of detection (LOD) for acridine measured with microchip APCI at flow rate of 6.2 muL/min was 5 nM, corresponding to a mass flow of 0.52 fmol/s. The LOD with commercial macro-APCI at a flow rate of 1 mL/min for acridine was the same, 5 nM, corresponding to a significantly worse mass flow sensitivity (83 fmol/s) than measured with microchip APCI. The advantages of microchip APCI makes it a very attractive new microfluidic detector. PMID:15538790

  1. Incoherent production reactions of positive and negative ions in matrix-assisted laser desorption/ionization.

    PubMed

    Liu, Bo-Hong; Lee, Yuan Tseh; Wang, Yi-Sheng

    2009-06-01

    Utilizing synchronized dual-polarity matrix-assisted laser desorption/ionization (MALDI) mass spectrometry, we found good evidence of the incoherent production of positive and negative matrix ions. Using thin, homogeneous 2,5-dehydroxybenzoic acid (DHB) matrix films, positive and negative matrix ions were found to appear at different threshold laser fluences. The presence of molecular matrix ions of single charge polarity suggests that the existence of DHB ion-pairs may not be a prerequisite in MALDI. Photoelectrons induced by the laser excitation may assist the production of negative DHB ions, as shown in experiments conducted with stainless steel and glass substrates. At high laser fluences, the relative yield of positive and negative matrix ions remained constant when homogeneous matrix films were used, but it fluctuated significantly with inhomogeneous crystal morphology. This result is also inconsistent with the hypothesis that matrix ion-pairs are essential primary ions. Evidence from both low and high laser fluences suggests that the productions of positive and negative matrix ions in MALDI may occur via independent pathways. PMID:19299167

  2. IonInduced Nucleation in Nanoparticle Synthesis by Ionization Chemical Vapor Deposition

    Microsoft Academic Search

    Motoaki Adachi; Masataka Kusumi; Shigeki Tsukui

    2004-01-01

    Particle formation mechanisms in nanoparticle synthesis by ionization chemical vapor deposition (CVD), in which source gases are ionized before being fed into the reactor, were investigated experimentally. First, nonagglomerated nanoparticles were formed from a tetraethylorthosilicate (TEOS)\\/O2 mixture ionized with a sonic-jet ionizer at various furnace temperatures, Tf, and TEOS concentrations, NTEOS. Then, the electrical mobility of the nanoparticles and ions

  3. The Effect of Salts on Electrospray Ionization of Amino Acids in the Negative Mode

    NASA Technical Reports Server (NTRS)

    Kim, H. I.; Johnson, P. V.; Beegle, L. W.; Kanik, I.

    2004-01-01

    The continued search for organics on Mars will require the development of simplified procedures for handling and processing of soil or rock core samples prior to analysis by onboard instrumentation. Extraction of certain organic molecules such as amino acids from rock and soil samples using a liquid solvent (H2O) has been shown to be more efficient (by approximately an order of magnitude) than heat extraction methods. As such, liquid extraction (using H2O) of amino acid molecules from rock cores or regolith material is a prime candidate for the required processing. In this scenario, electrospray ionization (ESI) of the liquid extract would be a natural choice for ionization of the analyte prior to interrogation by one of a variety of potential analytical separation techniques (mass spectroscopy, ion mobility spectroscopy, etc.). Aside from the obvious compatibility of ESI and liquid samples, ESI offers simplicity and a soft ionization capability. In order to demonstrate that liquid extraction and ESI can work as part of an in situ instrument on Mars, we must better understand and quantify the effect salts have on the ESI process. In the current work, we have endeavored to investigate the feasibility and limitations of negative mode ESI of Martian surface samples in the context of sample salt content using ion mobility spectroscopy (IMS).

  4. Sensitive monitoring of volatile chemical warfare agents in air by atmospheric pressure chemical ionization mass spectrometry with counter-flow introduction.

    PubMed

    Seto, Yasuo; Kanamori-Kataoka, Mieko; Tsuge, Koichiro; Ohsawa, Isaac; Iura, Kazumitsu; Itoi, Teruo; Sekiguchi, Hiroyuki; Matsushita, Koji; Yamashiro, Shigeharu; Sano, Yasuhiro; Sekiguchi, Hiroshi; Maruko, Hisashi; Takayama, Yasuo; Sekioka, Ryoji; Okumura, Akihiko; Takada, Yasuaki; Nagano, Hisashi; Waki, Izumi; Ezawa, Naoya; Tanimoto, Hiroyuki; Honjo, Shigeru; Fukano, Masumi; Okada, Hidehiro

    2013-03-01

    A new method for sensitively and selectively detecting chemical warfare agents (CWAs) in air was developed using counter-flow introduction atmospheric pressure chemical ionization mass spectrometry (MS). Four volatile and highly toxic CWAs were examined, including the nerve gases sarin and tabun, and the blister agents mustard gas (HD) and Lewisite 1 (L1). Soft ionization was performed using corona discharge to form reactant ions, and the ions were sent in the direction opposite to the airflow by an electric field to eliminate the interfering neutral molecules such as ozone and nitrogen oxide. This resulted in efficient ionization of the target CWAs, especially in the negative ionization mode. Quadrupole MS (QMS) and ion trap tandem MS (ITMS) instruments were developed and investigated, which were movable on the building floor. For sarin, tabun, and HD, the protonated molecular ions and their fragment ions were observed in the positive ion mode. For L1, the chloride adduct ions of L1 hydrolysis products were observed in negative ion mode. The limit of detection (LOD) values in real-time or for a 1 s measurement monitoring the characteristic ions were between 1 and 8 ?g/m(3) in QMS instrument. Collision-induced fragmentation patterns for the CWAs were observed in an ITMS instrument, and optimized combinations of the parent and daughter ion pairs were selected to achieve real-time detection with LOD values of around 1 ?g/m(3). This is a first demonstration of sensitive and specific real-time detection of both positively and negatively ionizable CWAs by MS instruments used for field monitoring. PMID:23339735

  5. Didehydro radical anions from ketones via O- chemical ionization

    NASA Astrophysics Data System (ADS)

    Lin, Mingxiang; Grabowski, Joseph J.

    2004-10-01

    Gas-phase ion-molecule reactions of the atomic oxygen radical anion, O- with selected ketones are investigated to explore a strategy to 1,3-distonic radical anions. These O- chemical ionization reactions, especially that of cyclopentanone, are examined in detail under the well-defined thermal energy conditions uniquely available by using the flowing afterglow technique. To further understanding of the reaction mechanism, a series of related ketones (acetone, 3-pentanone, 2-butanone, 2,4-dimethyl-3-pentanone, cyclohexanone) are also examined in detail. Rate constants for each ketone reaction are measured and products from each ketone examined are identified and their branching ratios are reported. Based on these results, a detailed reaction scheme for each ketone reaction studied is proposed. The individual reaction schemes are summarized in a composite O-/ketone reaction scheme and the specific reaction pathways are discussed. A strategy is developed to differentiate 1,1- and 1,3-H2+-abstraction products and to establish the absolute yields of 1,3-distonic radical anions from appropriate ketones.

  6. Emittance studies of high intensity negative ion sources equipped with continuous surface cylindrical and spherical geometry tungsten ionizers

    SciTech Connect

    Alton, G.D.; McConnell, J.W.; Tajima, S.; Nelson, G.S.

    1986-01-01

    A digitally controlled emittance measurement, data acquisition and processing system has been designed, implemented and used to determine emittances of negative ion beams extracted from high-intensity negative-ion sources equipped with cylindrical and spherical geometry cesium surface ionizers. Comparative studies indicate that the emittances of ion beams extracted from the source equipped with a spherical geometry ionizer are lower by 13% to 21% than those extracted from the source equipped with a cylindrical geometry ionizer. This difference may be attributable to geometric factors rather than differences in the sizes of the emission areas at the points of negative-ion generation. Studies reveal that the emittances of these sources are independent of ion mass for most of the materials investigated and independent of ion current over the range of ion currents used in these investigations (4..mu..A to 12 ..mu..A).

  7. Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

    PubMed

    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

    2014-05-01

    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. PMID:24678766

  8. Chemical abundances and properties of the ionized gas in NGC 1705

    E-print Network

    Annibali, F; Pasquali, A; Aloisi, A; Mignoli, M; Romano, D

    2015-01-01

    We obtained [O III] narrow-band imaging and multi-slit MXU spectroscopy of the blue compact dwarf (BCD) galaxy NGC 1705 with FORS2@VLT to derive chemical abundances of PNe and H II regions and, more in general, to characterize the properties of the ionized gas. The auroral [O III]\\lambda4363 line was detected in all but one of the eleven analyzed regions, allowing for a direct estimate of their electron temperature. The only object for which the [O III]\\lambda4363 line was not detected is a possible low-ionization PN, the only one detected in our data. For all the other regions, we derived the abundances of Nitrogen, Oxygen, Neon, Sulfur and Argon out to ~1 kpc from the galaxy center. We detect for the first time in NGC 1705 a negative radial gradient in the oxygen metallicity of -0.24 \\pm 0.08 dex kpc^{-1}. The element abundances are all consistent with values reported in the literature for other samples of dwarf irregular and blue compact dwarf galaxies. However, the average (central) oxygen abundance, 12 +...

  9. Plasma-chemical simulation of negative corona near the inception voltage

    NASA Astrophysics Data System (ADS)

    Pontiga, Francisco; Duran-Olivencia, Francisco J.; Castellanos, Antonio

    2013-09-01

    The spatiotemporal development of Trichel pulses in oxygen between a spherical electrode and a grounded plane has been simulated using a fluid approximation that incorporates the plasma chemistry of the electrical discharge. Elementary plasma processes, such as ionization, electron attachment, electron detachment, recombination between ions and chemical reactions between neutral species, are all included in a chemical model consisting of 55 reactions between 8 different species (electrons, O2+,O2-,O3-,O-, O2, O, O3). Secondary emission at the cathode by the impact of positive ions and photons is also considered. The spatial distribution of species is computed in three dimensions (2D-axysimmetrical) by solving Poisson's equation for the electric field and the continuity equations for the species, with the inclusion of the chemical gain/loss rate due to the particle interaction. The results of the simulation reveal the interplay between the different negative ions during the development of every Trichel pulse, and the rate of production of atomic oxygen and ozone by the corona discharge. The spatiotemporal development of Trichel pulses in oxygen between a spherical electrode and a grounded plane has been simulated using a fluid approximation that incorporates the plasma chemistry of the electrical discharge. Elementary plasma processes, such as ionization, electron attachment, electron detachment, recombination between ions and chemical reactions between neutral species, are all included in a chemical model consisting of 55 reactions between 8 different species (electrons, O2+,O2-,O3-,O-, O2, O, O3). Secondary emission at the cathode by the impact of positive ions and photons is also considered. The spatial distribution of species is computed in three dimensions (2D-axysimmetrical) by solving Poisson's equation for the electric field and the continuity equations for the species, with the inclusion of the chemical gain/loss rate due to the particle interaction. The results of the simulation reveal the interplay between the different negative ions during the development of every Trichel pulse, and the rate of production of atomic oxygen and ozone by the corona discharge. This work was supported by the Consejeria de Innovacion, Ciencia y Empresa (Junta de Andalucia) and by the Ministerio de Ciencia e Innovacion, Spain, within the European Regional Development Fund contracts FQM-4983 and FIS2011-25161.

  10. Ionization of Samarium by Chemical Releases in the Upper Atmosphere

    NASA Astrophysics Data System (ADS)

    Siefring, C. L.; Bernhardt, P. A.; Holmes, J. M.; Pedersen, T. R.; Caton, R.; Miller, D.; Groves, K. M.

    2014-12-01

    The release of Samarium vapor into the upper atmosphere was studied using during the Air Force Research Laboratory sponsored Metal Oxide Space Cloud (MOSC) rocket launches in May 2009. The Naval Research Laboratory supported these experiments with 3-D photochemical modeling of the artificial plasma cloud including (1) reactions with atomic oxygen, (2) photo excitation, (3) photoionization, (4) dissociative recombination, and (5) ion and neutral diffusion. NRL provided the experimental diagnostic instrument on the rocket which was a dual frequency radio beacon on the rocket to measure changes in total electron content. The AFRL provided ground based diagnostics of incoherent scatter radar and optical spectroscopy and imagery. The NRL Chemical Release Model (CRM) has over 600 excited states of atomic Samarium neutrals, atomic ions, along with Samarium Oxide Ions and electrons. Diffusive transport of neutrals in cylindrical geometry and ions along magnetic field lines is computed along with the reactive flow to predict the concentrations of Sm, Sm-Ion, Sm0, and SmO Ion. Comparison of the CRM with observations demonstrates that Sm release into the upper atmosphere initially produces enhanced electron densities and SmO-Ions. The diatomic ions recombine with electrons to yield neutral Sm and O. Only the photo ionization of Sm yields a stable atomic ion that does not substantially recombine. The MOSC releases in sunlight yielded long duration ion clouds that can be replicated with the CRM. The CRM predicts that Sm releases in darkness would not produce long duration plasma clouds because of the lack of photo excitation and photoionization.

  11. A study of the tropospheric oxidation of volatile organic compounds using chemical ionization mass spectrometry

    E-print Network

    Broekhuizen, Keith Edward, 1974-

    2002-01-01

    The mechanisms and kinetics of reactions important to the troposphere have been investigated using a high pressure, turbulent, discharge-flow technique coupled to a chemical ionization mass spectrometer. The ability to ...

  12. CHLORIDEDETERMINATION IN HIGH IONIC STRENGTH SOLUTION OF AMMONIUM ACETATE USING NEGATIVE ION ELECTRON SPRAY IONIZATION (HPLC/MS)

    EPA Science Inventory

    A precise ion chromatography method has been developed for the determination of chloride in high ionic strength ammonium acetate solutions (10-5 M-5 M) using sodium carbonate/sodium bicarbonate as eluent. Negative ion electrospray ionization (ESI) mass spectrometry was used for q...

  13. Mass spectrometric behavior of anabolic androgenic steroids using gas chromatography coupled to atmospheric pressure chemical ionization source. Part I: ionization.

    PubMed

    Raro, M; Portolés, T; Sancho, J V; Pitarch, E; Hernández, F; Marcos, J; Ventura, R; Gómez, C; Segura, J; Pozo, O J

    2014-06-01

    The detection of anabolic androgenic steroids (AAS) is one of the most important topics in doping control analysis. Gas chromatography coupled to (tandem) mass spectrometry (GC-MS(/MS)) with electron ionization and liquid chromatography coupled to tandem mass spectrometry have been traditionally applied for this purpose. However, both approaches still have important limitations, and, therefore, detection of all AAS is currently afforded by the combination of these strategies. Alternative ionization techniques can minimize these drawbacks and help in the implementation of a single method for the detection of AAS. In the present work, a new atmospheric pressure chemical ionization (APCI) source commercialized for gas chromatography coupled to a quadrupole time-of-flight analyzer has been tested to evaluate the ionization of 60 model AAS. Underivatized and trimethylsylil (TMS)-derivatized compounds have been investigated. The use of GC-APCI-MS allowed for the ionization of all AAS assayed irrespective of their structure. The presence of water in the source as modifier promoted the formation of protonated molecules ([M+H](+)), becoming the base peak of the spectrum for the majority of studied compounds. Under these conditions, [M+H](+), [M+H-H2O](+) and [M+H-2·H2O](+) for underivatized AAS and [M+H](+), [M+H-TMSOH](+) and [M+H-2·TMSOH](+) for TMS-derivatized AAS were observed as main ions in the spectra. The formed ions preserve the intact steroid skeleton, and, therefore, they might be used as specific precursors in MS/MS-based methods. Additionally, a relationship between the relative abundance of these ions and the AAS structure has been established. This relationship might be useful in the structural elucidation of unknown metabolites. PMID:24913403

  14. Identification of ground water contaminations by landfills using precise boron isotope ratio measurements with negative thermal ionization mass spectrometry

    Microsoft Academic Search

    S. Eisenhut; K. G. Heumann

    1997-01-01

    Precise boron isotope ratio measurements with negative thermal ionization mass spectrometry were used for the identification\\u000a of ground water contaminations by leakages of landfills. BO-\\u000a 2thermal ions were produced to determine the 11B\\/10B isotope ratio, which was expressed as ?11B value in ‰ normalized to the standard reference material NIST SRM 951. For example, household waste influences the boron\\u000a isotope

  15. CHEMICAL PROCESSES IN PROTOPLANETARY DISKS. II. ON THE IMPORTANCE OF PHOTOCHEMISTRY AND X-RAY IONIZATION

    SciTech Connect

    Walsh, Catherine; Millar, T. J. [Astrophysics Research Centre, School of Mathematics and Physics, Queen's University Belfast, University Road, Belfast BT7 1NN (United Kingdom); Nomura, Hideko [Department of Astronomy, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan); Aikawa, Yuri, E-mail: catherine.walsh@qub.ac.uk [Department of Earth and Planetary Sciences, Kobe University, 1-1 Rokkodai-cho, Nada, Kobe 657-8501 (Japan)

    2012-03-10

    We investigate the impact of photochemistry and X-ray ionization on the molecular composition of, and ionization fraction in, a protoplanetary disk surrounding a typical T Tauri star. We use a sophisticated physical model, which includes a robust treatment of the radiative transfer of UV and X-ray radiation, and calculate the time-dependent chemical structure using a comprehensive chemical network. In previous work, we approximated the photochemistry and X-ray ionization; here, we recalculate the photoreaction rates using the explicit UV wavelength spectrum and wavelength-dependent reaction cross sections. We recalculate the X-ray ionization rate using our explicit elemental composition and X-ray energy spectrum. We find that photochemistry has a larger influence on the molecular composition than X-ray ionization. Observable molecules sensitive to the photorates include OH, HCO{sup +}, N{sub 2}H{sup +}, H{sub 2}O, CO{sub 2}, and CH{sub 3}OH. The only molecule significantly affected by the X-ray ionization is N{sub 2}H{sup +}, indicating that it is safe to adopt existing approximations of the X-ray ionization rate in typical T Tauri star-disk systems. The recalculation of the photorates increases the abundances of neutral molecules in the outer disk, highlighting the importance of taking into account the shape of the UV spectrum in protoplanetary disks. A recalculation of the photoreaction rates also affects the gas-phase chemistry due to the adjustment of the H/H{sub 2} and C{sup +}/C ratios. The disk ionization fraction is not significantly affected by the methods adopted to calculate the photochemistry and X-ray ionization. We determine that there is a probable 'dead zone' where accretion is suppressed, present in a layer, Z/R {approx}< 0.1-0.2, in the disk midplane, within R Almost-Equal-To 200 AU.

  16. Alternately pulsed nanoelectrospray ionization/atmospheric pressure chemical ionization for ion/ion reactions in an electrodynamic ion trap.

    PubMed

    Liang, Xiaorong; Xia, Yu; McLuckey, Scott A

    2006-05-01

    The alternate operation of nanoelectrospray ionization and atmospheric pressure chemical ionization, using a common atmosphere/vacuum interface and ion path, has been implemented to facilitate ion/ion reaction experiments in a linear ion trap-based tandem mass spectrometer. The ion sources are operated in opposite polarity modes whereby one of the ion sources is used to form analyte ions while the other is used to form reagent ions of opposite polarity. This combination of ion sources is well-suited to implementation of experiments involving multiply charged ions in reaction with singly charged ions of opposite polarity. Three analytically useful ion/ion reaction types are illustrated: the partial deprotonation of a multiply protonated protein, the partial protonation of a multiply deprotonated oligonucleotide, and electron transfer to a multiply protonated peptide. The approach described herein is attractive in that it enables both single proton-transfer and single electron-transfer ion/ion reaction experiments to be implemented without requiring major modifications to the tandem mass spectrometer hardware. Furthermore, a wide range of reactant ions can be formed with these ionization methods and the pulsed nature of operation appears to lead to no significant compromise in the performance of either ion source. PMID:16643016

  17. Chemical Processes in Protoplanetary Disks II. On the importance of photochemistry and X-ray ionization

    E-print Network

    Walsh, Catherine; Millar, T J; Aikawa, Yuri

    2012-01-01

    We investigate the impact of photochemistry and X-ray ionization on the molecular composition of, and ionization fraction in, a protoplanetary disk surrounding a typical T Tauri star. We use a sophisticated physical model, which includes a robust treatment of the radiative transfer of UV and X-ray radiation, and calculate the time-dependent chemical structure using a comprehensive chemical network. In previous work, we approximated the photochemistry and X-ray ionization, here, we recalculate the photoreaction rates using the explicit UV wavelength spectrum and wavelength-dependent reaction cross sections. We recalculate the X-ray ionization rate using our explicit elemental composition and X-ray energy spectrum. We find photochemistry has a larger influence on the molecular composition than X-ray ionization. Observable molecules sensitive to the photorates include OH, HCO+, N2H+, H2O, CO2 and CH3OH. The only molecule significantly affected by the X-ray ionization is N2H+ indicating it is safe to adopt existi...

  18. Detection limits of electron and electron capture negative ionization-mass spectrometry for aldehydes derivatized with o -(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine hydrochloride

    Microsoft Academic Search

    Josef Beránek; Darrin A. Muggli; Alena Kubátová

    2010-01-01

    In contrast to common expectations, the differences in limits of detection (LODs) between electron capture negative ionization\\u000a (ECNI) and electron ionization (EI) mass spectrometry (MS) were found to be insignificant for a wide range of aldehydes derivatized\\u000a with o-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine hydrochloride. Comparison of the two ionization methods based on LOD confidence\\u000a intervals revealed that a traditional presentation of the LOD or

  19. Fundamentals of ambient metastable-induced chemical ionization mass spectrometry and atmospheric pressure ion mobility spectrometry

    NASA Astrophysics Data System (ADS)

    Harris, Glenn A.

    Molecular ionization is owed much of its development from the early implementation of electron ionization (EI). Although dramatically increasing the library of compounds discovered, an inherent problem with EI was the low abundance of molecular ions detected due to high fragmentation leading to the difficult task of the correct chemical identification after mass spectrometry (MS). These problems stimulated the research into new ionization methods which sought to "soften" the ionization process. In the late 1980s the advancements of ionization techniques was thought to have reached its pinnacle with both electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). Both ionization techniques allowed for "soft" ionization of large molecular weight and/or labile compounds for intact characterization by MS. Albeit pervasive, neither ESI nor MALDI can be viewed as "magic bullet" ionization techniques. Both techniques require sample preparation which often included native sample destruction, and operation of these techniques took place in sealed enclosures and often, reduced pressure conditions. New open-air ionization techniques termed "ambient MS" enable direct analysis of samples of various physical states, sizes and shapes. One particular technique named Direct Analysis In Real Time (DART) has been steadily growing as one of the ambient tools of choice to ionize small molecular weight (< 1000 Da) molecules with a wide range of polarities. Although there is a large list of reported applications using DART as an ionization source, there have not been many studies investigating the fundamental properties of DART desorption and ionization mechanisms. The work presented in this thesis is aimed to provide in depth findings on the physicochemical phenomena during open-air DART desorption and ionization MS and current application developments. A review of recent ambient plasma-based desorption/ionization techniques for analytical MS is presented in Chapter 1. Chapter 2 presents the first investigations into the atmospheric pressure ion transport phenomena during DART analysis. Chapter 3 provides a comparison on the internal energy deposition processes during DART and pneumatically assisted-ESI. Chapter 4 investigates the complex spatially-dependent sampling sensitivity, dynamic range and ion suppression effects present in most DART experiments. New implementations and applications with DART are shown in Chapters 5 and 6. In Chapter 5, DART is coupled to multiplexed drift tube ion mobility spectrometry as a potential fieldable platform for the detection of toxic industrial chemicals and chemical warfare agents simulants. In Chapter 6, transmission-mode DART is shown to be an effective method for reproducible sampling from materials which allow for gas to flow through it. Also, Chapter 6 provides a description of a MS imaging platform coupling infrared laser ablation and DART-like phenomena. Finally, in Chapter 7 I will provide perspective on the work completed with DART and the tasks and goals that future studies should focus on.

  20. Characterization of Nitrogen-Containing Species in Coal andPetroleum-Derived Products by ammonia Chemical Ionization-High Resolution MassSpectrometry.

    SciTech Connect

    None

    1997-01-01

    A coal-derived light distillate and a petroleum-derived residuum have been studied by high resolution mass spectrometry using both low-pressure ammonia chemical ionization and low-voltage electron impact ionization. A mass calibration mixture for use with ammonia chemical ionization has been developed. Selective ionization of the basic nitrogen-containing compounds by ammonia chemical ionization and compound type characterization of the resulting quasi-molecular species has been demonstrated. Several homologous series of nitrogen-containing compounds were identified in a basic extract by electron impact ionization and compared with quasimolecular analogs identified by ammonia chemical ionization.

  1. Kinetics and continuum emission of negative atomic ions in partially ionized plasmas

    NASA Technical Reports Server (NTRS)

    Soon, W. H.; Kunc, J. A.

    1991-01-01

    Kinetics and continuum emission of negative ions are studied in stationary atomic hydrogen, nitrogen, and oxygen plasmas. The intensity of the negative-ion emission was found to be neglibible when compared to those of bound-bound and free-bound emission at low and medium particle densities. However, the negative-ion continuum emission can contribute significantly in certain parts of the emission spectrum at high particle densities.

  2. On the dynamics of chemical reactions of negative ions

    E-print Network

    Mikosch, Jochen; Wester, Roland

    2010-01-01

    This review discusses the dynamics of negative ion reactions with neutral molecules in the gas phase. Most anion-molecule reactions proceed via a qualitatively different interaction potential than cationic or neutral reactions. It has been and still is the goal of many experiments to understand these reaction dynamics and the different reaction mechanisms they lead to. We will show how rate coefficients and cross sections for anion-molecule reactions are measured and interpreted to yield information on the underlying dynamics. We will also present more detailed approaches that study either the transient reaction complex or the energy- and angle-resolved scattering of negative ions with neutral molecules. With the help of these different techniques many aspects of anion-molecule reaction dynamics could be unravelled in the last years. However, we are still far from a complete understanding of the complex molecular interplay that is at work during a negative ion reaction.

  3. Gaseous composition measured by a chemical ionization mass spectrometer in fresh and aged ship plumes

    NASA Astrophysics Data System (ADS)

    Faxon, Cameron; Psichoudaki, Magda; Kuuluvainen, Heino; Hallquist, Åsa; Thomson, Erik; Pettersson, Jan; Hallquist, Mattias

    2015-04-01

    The port of Gothenburg is the largest port of the Nordic countries with numerous ships calling the port daily. The ship exhausts contain numerous pollutants including gases such as SO2 and NOx as well as particulate matter and soot. The exhaust also contains numerous organic compounds, a large fraction of which are unidentified. These organics are oxidized in the atmosphere producing more oxygenated and potentially less volatile compounds that may contribute to the secondary organic aerosol (SOA). This work focuses on the characterization of fresh gaseous species present in the exhaust plumes of the passing ships and also on their photochemical aging. Between 26 September and 12 November 2014 measurements were conducted at a sampling site located on a small peninsula at the entrance of Gothenburg's port. The campaign was divided in two periods. During the first period, the fresh plumes of the passing ships were measured through a main inlet. During the second period, the sample passed through the same inlet and was then introduced into a Potential Aerosol Mass (PAM) reactor. The PAM reactor uses UV lamps and high concentrations of oxidants (OH radicals and O3) to oxidize the organic species present in the plumes. The oxidation that takes place within the reactor can be equivalent to up to one week of atmospheric oxidation. Preliminary tests showed that the oxidation employed in the current camping corresponded to 3.4 days in the atmosphere. A Time-of-Flight Chemical Ionization Mass Spectrometer (ToF-CIMS) was employed to monitor the concentration of different organic species present in the fresh and aged plumes. Water (positive) and iodide (negative) ionization methods were employed were water was primarily used for fresh plumes (large fraction of non-polar compounds) while iodide was used for the aged plumes (primarily oxidised products). The H2O, O3 and SO2 concentrations inside the PAM chamber were monitored, and an organic tracer for OH exposure determination was also continuously measured. The dominant species concentrations of both fresh and aged ship plumes are presented and their emission factors are estimated from concurrent CO2 measurements.

  4. Atmospheric pressure chemical ionization of explosives using alternating current corona discharge ion source.

    PubMed

    Usmanov, Dilshadbek Tursunbaevich; Chen, Lee Chuin; Yu, Zhan; Yamabe, Shinichi; Sakaki, Shigeyoshi; Hiraoka, Kenzo

    2015-04-01

    Ensuring public safety and security in today's mobile society requires robust detection technologies that are field-deployable and offer ever-improving sensitivity and specificity. Atmospheric pressure ionization is well suited to field-based sampling but pumping requirements to offset high gas loads can restrict an instrument's deployability and detection sensitivity. In the Special Feature, Usmanov and co-workers describe improved detection for nitrogen-containing explosive compounds using Atmospheric Pressure Chemical Ionization with an alternating current corona discharge source. An electromolded capillary yields a more stable ac corona allowing it to be positioned within 1mm from the inlet for detection limits in the tens of pg. PMID:26149117

  5. Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

    Microsoft Academic Search

    G. A. Eiceman; J. F. Bergloff; J. E. Rodriguez; W. Munro; Z. Karpas

    1999-01-01

    Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5?x\\u000a F\\u000a x\\u000a OH where x=0–5) in nitrogen with Cl? as the reagent ion yielded product ions of M·Cl? through ion associations or (M?H)? through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting\\u000a that some proton abstraction occurs through collision induced dissociation (CID)

  6. Fragmentation of allylmethylsulfide by chemical ionization: dependence on humidity and inhibiting role of water.

    PubMed

    Maihom, Thana; Schuhfried, Erna; Probst, Michael; Limtrakul, Jumras; Märk, Tilmann D; Biasioli, Franco

    2013-06-20

    We report on a previously unknown reaction mechanism involving water in the fragmentation reaction following chemical ionization. This result stems from a study presented here on the humidity-dependent and energy-dependent endoergic fragmentation of allyl methyl sulfide (AMS) upon protonation in a proton transfer reaction-mass spectrometer (PTR-MS). The fragmentation pathways were studied with experimental (PTR-MS) and quantum chemical methods (polarizable continuum model (PCM), microhydration, studied at the MP2/6-311+G(3df,2p)//MP2/6-31G(d,p) level of theory). We report in detail on the energy profiles, reaction mechanisms, and proton affinities (G4MP2 calculations). In the discovered reaction mechanism, water reduces the fragmentation of protonated species in chemical ionization. It does so by direct interaction with the protonated species via covalent binding (C3H5(+)) or via association (AMS·H(+)). This stabilizes intermediate complexes and thus overall increases the activation energy for fragmentation. Water thereby acts as a reusable inhibitor (anticatalyst) in chemical ionization. Moreover, according to the quantum chemical (QC) results, when water is present in abundance it has the opposite effect and enhances fragmentation. The underlying reason is a concentration-dependent change in the reaction principle from active inhibition of fragmentation to solvation, which then enhances fragmentation. This amphoteric behavior of water is found for the fragmentation of C3H5(+) to C3H3(+), and similarly for the fragmentation of AMS·H(+) to C3H5(+). The results support humidity-dependent quantification efforts for PTR-MS and chemical ionization mass spectrometry (CIMS). Moreover, the results should allow for a better understanding of ion-chemistry in the presence of water. PMID:23682687

  7. Negative base current and impact ionization phenomena in AlGaAs\\/GaAs HBTs

    Microsoft Academic Search

    Enrico Zanoni; Roger Malik; Paolo Pavan; Julien Nagle; Alessandro Paccagnella; Claudio Canali

    1992-01-01

    Impact ionization phenomena in the collector region of AlGaAs\\/GaAs heterojunction bipolar transistors give rise to base current reduction and reversal. These phenomena can be characterized by extracting the M-1 coefficient, which can be evaluated by measuring base current changes. Measurements of M-1 are affected at low current densities by the presence of the collector-base junction reverse current ICBO. At high

  8. Characterization of phthalides in Ligusticum chuanxiong by liquid chromatographic-atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Zhang, Xiaozhe; Xiao, Hongbin; Xu, Qing; Li, Xiuling; Wang, Jianing; Liang, Xinmiao

    2003-09-01

    High-performance liquid chromatography (HPLC) with diode-array detection interfaced to atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) is applied to analyze phthalides from Chuanxiong (the rhizome of Ligusticum chuanxiong). This herb material, containing plenty of phthalide compositions, is selected as the analytical target in this paper for its hematological activity. Some of the phthalides are not stable and are difficult to analyze by gas chromatography-MS. Under optimized LC-MS-MS conditions, six phthalides in the methanol extract of Chuanxiong are unambiguously identified, and characteristic fragments are obtained using homemade reference standards. Ten other phthalides in the extract are confirmed by means of LC-APCI-MS with positive-negative ion mode and collision-induced dissociation in combination with UV spectrophotometry. The results show that LC-MS-MS is a method of choice for fast detection and detailed structural analysis of such mixtures in the crude extract of Chuanxiong. PMID:14558936

  9. Negative air ions as a source of superoxide

    Microsoft Academic Search

    Naum I. Goldstein; Roman N. Goldstein; Mark N. Merzlyak

    1992-01-01

    The physico-chemical characteristics and possible formation mechanisms of negative air ions are considered. It was found that the products of oxygen and nitrogen negative ionization reduce ferricytochromec and nitroblue tetrazolium, and that these reactions were inhibited by superoxide dismutase. The interaction of negatively ionized oxygen with water led to hydrogen peroxide accumulation, which was inhibited by tetranitromethane or catalase. Nitrogen

  10. Alternative Methodology for Boron Isotopic Analysis of CaCO3 by Negative Thermal Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Dwyer, G. S.; Vengosh, A.

    2012-12-01

    Negative thermal ionization mass spectrometry (NTIMS) has been a common tool for investigating boron isotopes in CaCO3 and other environmental samples, the high sensitivity of BO2- ionization enabling measurements of ng levels of boron. However, B isotope measurement by this technique suffers from a number of problems, including: (1) fractionation induced by selective ionization of B isotopes in the mass spectrometer; (2) CNO- interference on mass 42 ([10BO2]-) that may be present in some filament load solutions (such as B-free seawater processed through ion-exchange resin), and (3) potential matrix effects due to widely differing chemistry of samples and standards. Here we examine a potentially improved NTIMS methodology that incudes removal of sample-related calcium (and other cations) by ion exchange and uses an alternative filament loading solution prepared from high-purity single-element solutions of Ca, Mg, Na, and K. Initial results suggest that this new method may offer significant improvement over the more traditional NTIMS approach in which digested CaCO3 samples are directly loaded onto filaments in B-free seawater. Replicate analyses of standards and samples yield a typical standard deviation of approximately 0.3‰ ?11B and boron isotopic compositions comparable to reported or consensus values. Fractionation during analysis has thus far typically been less than 0.5‰ ?11B. The method delivers boron ionization efficiency similar to directly-loaded seawater, and negligible signal at mass 26 (CN-), a proxy for the possible interfering molecular CNO- ion. Standards and samples behave similarly and predictably during filament heating and analysis, thus allowing for fully automated data acquisition, which in turn may increase sample throughput and reduce potential analytical inconsistencies associated with operator-controlled heating and analysis.

  11. Radioimmunoassay and chemical ionization/mass spectrometry compared for plasma cortisol determination

    SciTech Connect

    Lindberg, C. (AB Draco, Lund, Sweden); Johnson, S.; Hedner, P.; Gustafsson, A.

    1982-01-01

    A method is described for determination of cortisol in plasma and urine, based on chemical ionization/mass spectrometry with deuterium-labeled cortisol as the internal standard. The within-run precision (CV) was 2.5-5.7%, the between-run precision 4.6%. Results by this method were compared with those by a radioimmunological method (RIANEN Cortisol, New England Nuclear) for 395 plasma samples. The latter method gave significantly higher (approx. 25%) cortisol values.

  12. Real-time monitoring of volatile organic compounds using chemical ionization mass spectrometry

    DOEpatents

    Mowry, Curtis Dale (Albuquerque, NM); Thornberg, Steven Michael (Peralta, NM)

    1999-01-01

    A system for on-line quantitative monitoring of volatile organic compounds (VOCs) includes pressure reduction means for carrying a gaseous sample from a first location to a measuring input location maintained at a low pressure, the system utilizing active feedback to keep both the vapor flow and pressure to a chemical ionization mode mass spectrometer constant. A multiple input manifold for VOC and gas distribution permits a combination of calibration gases or samples to be applied to the spectrometer.

  13. Electron impact and chemical ionization mass spectral analysis of a volatile uranyl derivative

    SciTech Connect

    Reutter, D.J.; Hardy, D.R.

    1981-01-01

    Quadrupole mass spectral analysis of the volatile uranium ligand complex bis (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) dioxouranium-di-n-butyl sulfoxide is described utilizing electron impact (EI) and methane chemical ionization (CI) ion sources. All major ions are tentatively identified and the potential usefulness of this complex for determining uranium isotope /sup 235/U//sup 238/U abundance is demonstrated.

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

    Microsoft Academic Search

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

    2007-01-01

    We investigated how chemical equilibria are affected by the electrospray process, using simultaneous in situ measurements\\u000a by laser-induced fluorescence (LIF) and phase Doppler anemometry (PDA). The motivation for this study was the increasing number\\u000a of publications in which electrospray ionization mass spectrometry is used for binding constant determination. The PDA was\\u000a used to monitor droplet size and velocity, whereas LIF

  15. Differentiation of commercial fuels based on polar components using negative electrospray ionization/mass spectrometry

    USGS Publications Warehouse

    Rostad, C.E.

    2006-01-01

    Polar components in fuels may enable differentiation between fuel types or commercial fuel sources. A range of commercial fuels from numerous sources were analyzed by flow injection analysis/electrospray ionization/mass spectrometry without extensive sample preparation, separation, or chromatography. This technique enabled screening for unique polar components at parts per million levels in commercial hydrocarbon products, including a range of products from a variety of commercial sources and locations. Because these polar compounds are unique in different fuels, their presence may provide source information on hydrocarbons released into the environment. This analysis was then applied to mixtures of various products, as might be found in accidental releases into the environment. Copyright ?? Taylor & Francis Group, LLC.

  16. DETERMINATION OF PHTHALATES IN WATER AND SOIL BY TANDEM MASS SPECTROMETRY UNDER CHEMICAL IONIZATION CONDITIONS WITH ISOBUTANE AS REAGENT GAS

    EPA Science Inventory

    Phthalate determination is important because phthalates often are major impurities in samples and can have significant health effects. Tandem mass spectrometry under chemical ionization mass spectrometry conditions with isobutane as the reagent gas was used to determine 11 phthal...

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

    PubMed Central

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

    2010-01-01

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

  18. Gas chromatography-microchip atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Ostman, Pekka; Luosujärvi, Laura; Haapala, Markus; Grigoras, Kestas; Ketola, Raimo A; Kotiaho, Tapio; Franssila, Sami; Kostiainen, Risto

    2006-05-01

    An atmospheric pressure chemical ionization (APCI) microchip is presented for combining a gas chromatograph (GC) to a mass spectrometer (MS). The chip includes capillary insertion channel, stopper, vaporizer channel, nozzle and nebulizer gas inlet fabricated on the silicon wafer, and a platinum heater sputtered on a glass wafer. These two wafers are joined by anodic bonding creating a two-dimensional version of an APCI microchip. The sample from GC is directed via heated transfer line capillary to the vaporizer channel of the APCI chip. The etched nozzle forms narrow sample plume, which is ionized by an external corona discharge needle, and the ions are analyzed by a mass spectrometer. The GC-microchip APCI-MS combination provides an efficient method for qualitative and quantitative analysis. The spectra produced by microchip APCI show intensive protonated molecule and some fragmentation products as in classical chemical ionization for structure elucidation. In quantitative analysis the GC-microchip APCI-MS showed good linearity (r(2) = 0.9989) and repeatability (relative standard deviation 4.4%). The limits of detection with signal-to-noise ratio of three were between 0.5 and 2 micromol/L with MS mode using selected ion monitoring and 0.05 micromol/L with MS/MS using multiple reaction monitoring. PMID:16642989

  19. Negative electrospray ionization mass spectrometry: a method for sequencing and determining linkage position in oligosaccharides from branched hemicelluloses.

    PubMed

    Quéméner, Bernard; Vigouroux, Jacqueline; Rathahao, Estelle; Tabet, Jean Claude; Dimitrijevic, Aleksandra; Lahaye, Marc

    2015-01-01

    Xyloglucans of apple, tomato, bilberry and tamarind were hydrolyzed by commercial endo ?-1-4-D-endoglucanase. The xylo-gluco-oligosaccharides (XylGos) released were separated on CarboPac PA 200 column in less than 15?min, and, after purification, they were structurally characterized by negative electrospray ionization mass spectrometry using a quadrupole time-of-flight (ESI-Q-TOF), a hybrid linear ion trap (LTQ)/Orbitrap and a hybrid quadrupole Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometers. In order to corroborate the fragmentation routes observed on XylGos, some commercial galacto-manno-oligosaccharides (GalMOs) and glucurono-xylo-oligosaccharides were also studied. The fragmentation pathways of the ionized GalMos were similar to those of XylGos ones. The product ion spectra were mainly characterized by prominent double cleavage (D) ions corresponding to the entire inner side chains. The directed fragmentation from the reducing end to the other end was observed for the main glycosylated backbone but also for the side-chains, allowing their complete sequencing. Relevant cross-ring cleavage ions from (0,2)X(j)-type revealed to be diagnostic of the 1-2-linked- glycosyl units from XylGos together with the 1-2-linked glucuronic acid unit from glucuronoxylans. Resonant activation in the LTQ Orbitrap allowed not only determining the type of all linkages but also the O-acetyl group location on fucosylated side-chains. Moreover, the fragmentation of the different side chains using the MS(n) capabilities of the LTQ/Orbitrap analyzer also allowed differentiating terminal arabinosyl and xylosyl substituents inside S and U side-chains of XylGos, respectively. The CID spectra obtained were very informative for distinction of isomeric structures differing only in their substitution pattern. These features together makes the fragmentation in negative ionization mode a relevant and powerful technique useful to highlight the subtle structural changes generally observed during the development of plant organs such as during fruit ripening and for the screening of cell wall mutants with altered hemicellulose structure. PMID:25601700

  20. Carbon disulfide reagent allows the characterization of nonpolar analytes by atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Owen, Benjamin C; Gao, Jinshan; Borton, David J; Amundson, Lucas M; Archibold, Enada F; Tan, Xiaoli; Azyat, Khalid; Tykwinski, Rik; Gray, Murray; Kenttämaa, Hilkka I

    2011-07-30

    While atmospheric pressure ionization methodologies have revolutionized the mass spectrometric analysis of nonvolatile analytes, limitations native to the chemistry of these methodologies hinder or entirely inhibit the analysis of certain analytes, specifically, many nonpolar compounds. Examination of various analytes, including asphaltene and lignin model compounds as well as saturated hydrocarbons, demonstrates that atmospheric pressure chemical ionization (APCI) using CS(2) as the reagent produces an abundant and stable molecular ion (M(+•)) for all model compounds studied, with the exception of completely saturated aliphatic hydrocarbons and the two amino acids tested, arginine and phenylalanine. This reagent substantially broadens the applicability of mass spectrometry to nonvolatile nonpolar analytes and also facilitates the examination of radical cation chemistry by mass spectrometry. PMID:21698674

  1. Typing of Blood-Group Antigens on Neutral Oligosaccharides by Negative-Ion Electrospray Ionization Tandem Mass Spectrometry

    PubMed Central

    Zhang, Hongtao; Zhang, Shuang; Tao, Guanjun; Zhang, Yibing; Mulloy, Barbara; Zhan, Xiaobei; Chai, Wengang

    2013-01-01

    Blood-group antigens, such as those containing fucose and bearing the ABO(H)- and Lewis-type determinants expressed on the carbohydrate chains of glycoproteins and glycolipids, and also on unconjugated free oligosaccharides in human milk and other secretions, are associated with various biological functions. We have previously shown the utility of negative-ion electrospay ionization tandem mass spectrometry with collision-induced dissociation (ESI-CID-MS/MS) for typing of Lewis (Le) determinants, e.g. Lea, Lex, Leb, and Ley on neutral and sialylated oligosaccharide chains. In the present report we extended the strategy to characterization of blood-group A-, B- and H-determinants on type 1 and type 2, and also on type 4 globoside chains to provide a high sensitivity method for typing of all the major blood-group antigens, including the A, B, H, Lea, Lex, Leb, and Ley determinants, present in oligosaccharides. Using the principles established we identified two minor unknown oligosaccharide components present in the products of enzymatic synthesis by bacterial fermentation. We also demonstrated that the unique fragmentations derived from the D- and 0,2A-type cleavages observed in ESI-CID-MS/MS, which are important for assigning blood-group and chain types, only occur under the negative-ion conditions for reducing sugars but not for reduced alditols or under positive-ion conditions. PMID:23692402

  2. Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

    NASA Technical Reports Server (NTRS)

    Eiceman, G. A.; Bergloff, J. F.; Rodriguez, J. E.; Munro, W.; Karpas, Z.

    1999-01-01

    Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.

  3. Negative Electron Affinity Effect on the Surface of Chemical Vapor Deposited Diamond Polycrystalline Films

    NASA Technical Reports Server (NTRS)

    Krainsky, I. L.; Asnin, V. M.; Mearini, G. T.; Dayton, J. A., Jr.

    1996-01-01

    Strong negative electron affinity effects have been observed on the surface of as-grown chemical vapor deposited diamond using Secondary Electron Emission. The test samples were randomly oriented and the surface was terminated with hydrogen. The effect appears as an intensive peak in the low energy part of the spectrum of the electron energy distribution and may be described in the model of effective negative electron affinity.

  4. Chemical derivatization for electrospray ionization mass spectrometry. 1. Alkyl halides, alcohols, phenols, thiols, and amines

    SciTech Connect

    Quirke, J.M.E.; Adams, C.L.; Van Berkel, G.J. (Oak Ridge National Lab., TN (United States))

    1994-04-15

    Derivatization strategies and specific derivatization reactions for conversion of simple alkyl halides, alcohols, phenols, thiols, and amines to ionic or solution-ionizable derivatives, that is [open quotes]electrospray active[close quotes] (ES-active) forms of the analyte, are presented. Use of these reactions allows detection of analytes among those listed that are not normally amenable to analysis by electrospray ionization mass spectrometry (ES-MS). In addition, these reactions provide for analysis specificity and flexibility through functional group specific derivatization and through the formation of derivatives that can be detected in positive ion or in negative ion mode. For a few of the functional groups, amphoteric derivatives are formed that can be analyzed in either positive or negative ion modes. General synthetic strategies for transformation of members of these five compound classes to ES-active species are presented along with illustrative examples of suitable derivatives. Selected derivatives were prepared using model compounds and the ES mass spectra obtained for these derivatives are discussed. The analytical utility of derivatization for ES-MS analysis is illustrated in three experiments: (1) specific detection of the major secondary alcohol in oil of peppermint, (2) selective detection of phenols within a synthetic mixture of phenols, and (3) identification of the medicinal amines within a commercially available cold medication as primary, secondary or tertiary. 65 refs., 3 figs., 3 tabs.

  5. Bio-oil Analysis Using Negative Electrospray Ionization: Comparative Study of High-Resolution Mass Spectrometers and Phenolic versus Sugaric Components

    SciTech Connect

    Smith, Erica A.; Park, Soojin; Klein, Adam T.; Lee, Young Jin

    2012-05-16

    We have previously demonstrated that a petroleomic analysis could be performed for bio-oils and revealed the complex nature of bio-oils for the nonvolatile phenolic compounds (Smith, E.; Lee, Y. J. Energy Fuels 2010, 24, 5190?5198). As a subsequent study, we have adapted electrospray ionization in negative-ion mode to characterize a wide variety of bio-oil compounds. A comparative study of three common high-resolution mass spectrometers was performed to validate the methodology and to investigate the differences in mass discrimination and resolution. The mass spectrum is dominated by low mass compounds with m/z of 100–250, with some compounds being analyzable by gas chromatography–mass spectrometry (GC–MS). We could characterize over 800 chemical compositions, with only about 40 of them being previously known in GC–MS. This unveiled a much more complex nature of bio-oils than typically shown by GC–MS. The pyrolysis products of cellulose and hemicellulose, particularly polyhydroxy cyclic hydrocarbons (or what we call “sugaric” compounds), such as levoglucosan, could be effectively characterized with this approach. Phenolic compounds from lignin pyrolysis could be clearly distinguished in a contour map of double bond equivalent (DBE) versus the number of carbons from these sugaric compounds.

  6. Picoelectrospray ionization mass spectrometry using narrow-bore chemically etched emitters

    PubMed Central

    Marginean, Ioan; Tang, Keqi; Smith, Richard D.; Kelly, Ryan T.

    2013-01-01

    Electrospray ionization mass spectrometry (ESI-MS) at flow rates below ~10 nL/min has been only sporadically explored due to difficulty in reproducibly fabricating emitters that can operate at lower flow rates. Here we demonstrate narrow orifice chemically etched emitters for stable electrospray at flow rates as low as 400 pL/min. Depending on the analyte concentration, we observe two types of MS signal response as a function of flow rate. At low concentrations, an optimum flow rate is observed slightly above 1 nL/min, while the signal decreases monotonically with decreasing flow rates at higher concentrations. For example, consumption of 500 zmol of sample yielded signal-to-noise ratios ~10 for some peptides. In spite of lower MS signal, the ion utilization efficiency increases exponentially with decreasing flow rate in all cases. Significant variations in ionization efficiency were observed within this flow rate range for an equimolar mixture of peptides, indicating that ionization efficiency is an analyte-dependent characteristic for the present experimental conditions. Mass-limited samples benefit strongly from the use of low flow rates and avoiding unnecessary sample dilution. These findings have important implications for the analysis of trace biological samples. PMID:24122304

  7. Real time monitoring of accelerated chemical reactions by ultrasonication-assisted spray ionization mass spectrometry.

    PubMed

    Lin, Shu-Hsuan; Lo, Ta-Ju; Kuo, Fang-Yin; Chen, Yu-Chie

    2014-01-01

    Ultrasonication has been used to accelerate chemical reactions. It would be ideal if ultrasonication-assisted chemical reactions could be monitored by suitable detection tools such as mass spectrometry in real time. It would be helpful to clarify reaction intermediates/products and to have a better understanding of reaction mechanism. In this work, we developed a system for ultrasonication-assisted spray ionization mass spectrometry (UASI-MS) with an ~1.7 MHz ultrasonic transducer to monitor chemical reactions in real time. We demonstrated that simply depositing a sample solution on the MHz-based ultrasonic transducer, which was placed in front of the orifice of a mass spectrometer, the analyte signals can be readily detected by the mass spectrometer. Singly and multiply charged ions from small and large molecules, respectively, can be observed in the UASI mass spectra. Furthermore, the ultrasonic transducer used in the UASI setup accelerates the chemical reactions while being monitored via UASI-MS. The feasibility of using this approach for real-time acceleration/monitoring of chemical reactions was demonstrated. The reactions of Girard T reagent and hydroxylamine with steroids were used as the model reactions. Upon the deposition of reactant solutions on the ultrasonic transducer, the intermediate/product ions are readily generated and instantaneously monitored using MS within 1 s. Additionally, we also showed the possibility of using this reactive UASI-MS approach to assist the confirmation of trace steroids from complex urine samples by monitoring the generation of the product ions. PMID:24446263

  8. Laser Microdissection and Atmospheric Pressure Chemical Ionization Mass Spectrometry Coupled for Multimodal Imaging

    SciTech Connect

    Lorenz, Matthias [ORNL; Ovchinnikova, Olga S [ORNL; Kertesz, Vilmos [ORNL; Van Berkel, Gary J [ORNL

    2013-01-01

    This paper describes the coupling of ambient laser ablation surface sampling, accomplished using a laser capture microdissection system, with atmospheric pressure chemical ionization mass spectrometry for high spatial resolution multimodal imaging. A commercial laser capture microdissection system was placed in close proximity to a modified ion source of a mass spectrometer designed to allow for sampling of laser ablated material via a transfer tube directly into the ionization region. Rhodamine 6G dye of red sharpie ink in a laser etched pattern as well as cholesterol and phosphatidylcholine in a cerebellum mouse brain thin tissue section were identified and imaged from full scan mass spectra. A minimal spot diameter of 8 m was achieved using the 10X microscope cutting objective with a lateral oversampling pixel resolution of about 3.7 m. Distinguishing between features approximately 13 m apart in a cerebellum mouse brain thin tissue section was demonstrated in a multimodal fashion including co-registered optical and mass spectral chemical images.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Charge enhancement of single-stranded DNA in negative electrospray ionization using the supercharging reagent meta-nitrobenzyl alcohol.

    PubMed

    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. PMID:24030289

  11. Gas chromatography-electron ionization and chemical ionization mass spectrometric analysis of urinary phenmetrazine after derivatization with 4-carbethoxyhexafluorobutyryl chloride--a new derivative.

    PubMed

    Dasgupta, A; Hart, A; Humphrey, P; Blackwell, W

    1998-05-01

    Phenmetrazine is a central nervous system stimulant currently used as an anorectic agent. The drug is abused and is reported to cause death from overdose. We describe a new derivatization method for phenmetrazine using 4-carbethoxyhexafluorobutyryl chloride. Quantitation of urinary phenmetrazine can be easily achieved by using N-ethyl amphetamine as an internal standard. The electron ionization mass spectrum of 4-carbethoxyhexafluorobutyryl derivative of phenmetrazine showed a molecular ion at m/z 427 and a base peak at m/z 70. In the methane chemical ionization mass spectrum, the base peak was observed at m/z 428 (protonated molecular ion). In the electron ionization mass spectrum of 4-carbethoxyhexafluorobutyryl derivative of the internal standard, N-ethyl amphetamine we did not observe a molecular ion. However, in the chemical ionization mass spectrum, the protonated molecular ion at m/z 414 was the base peak. The retention time of derivatized phenmetrazine (8.4 min) was substantially longer than the retention time of the underivatized molecule. Moreover, underivatized phenmetrazine showed poor peak shape (substantial tailing) while derivatized phenmetrazine had excellent chromatographic properties. The within-run and between-run precisions of the assay were 2.6% and 3.1% respectively at a urinary phenmetrazine concentration of 10 micrograms/mL. The assay was linear for urinary phenmetrazine concentration of 1 to 100 micrograms/mL with a detection limit of 0.2 microgram/mL. PMID:9608702

  12. Physically consistent simulation of mesoscale chemical kinetics: The non-negative FIS-{alpha} method

    SciTech Connect

    Dana, Saswati, E-mail: saswatid@rishi.serc.iisc.ernet.in [Supercomputer Education and Research Centre, Indian Institute of Science, Bangalore 560012 (India); Raha, Soumyendu, E-mail: raha@serc.iisc.ernet.in [Supercomputer Education and Research Centre, Indian Institute of Science, Bangalore 560012 (India)

    2011-10-01

    Biochemical pathways involving chemical kinetics in medium concentrations (i.e., at mesoscale) of the reacting molecules can be approximated as chemical Langevin equations (CLE) systems. We address the physically consistent non-negative simulation of the CLE sample paths as well as the issue of non-Lipschitz diffusion coefficients when a species approaches depletion and any stiffness due to faster reactions. The non-negative Fully Implicit Stochastic {alpha} (FIS {alpha}) method in which stopped reaction channels due to depleted reactants are deleted until a reactant concentration rises again, for non-negativity preservation and in which a positive definite Jacobian is maintained to deal with possible stiffness, is proposed and analysed. The method is illustrated with the computation of active Protein Kinase C response in the Protein Kinase C pathway.

  13. Chemical and statistical considerations in the determination of partition coefficients of weakly ionizable drugs and poisons.

    PubMed

    Opong-Mensah, K; Woller, T W; Obaseki, A O; Porter, W R

    1984-01-01

    Equations have been developed that relate the concentration (or a parameter directly proportional to concentration, such as optical absorbance) of a weakly ionizable solute in a water-immiscible phase, in equilibrium with an aqueous phase, to the pH of the aqueous phase, the partition coefficient of the unionized solute and the phase volume ratio. These relationships have been used in the design of experimental methods for determining partition coefficients, which require measurement of solute concentration in only one phase. Data obtained in this way permit ready recognition of deviations from assumptions made in the development of the model; these assumptions include insolubility of the ionized solute in the water-immiscible phase and lack of interaction between buffer components and solute. Conditions for optimal liquid-liquid extraction of weakly ionizable solutes are more easily recognized. With these techniques, the negative logarithm of the acid dissociation constant (pK'a) and the logarithm of the octanol-water partition coefficient (log P) have been measured for warfarin (pK'a = 5.15 +/- 0.04; log P = 2.82 +/- 0.06), strychnine (pK'a = 8.29 +/- 0.02; log P = 2.23 +/- 0.04), phenol (pK'a = 9.88 +/- 0.02; log P = 1.75 +/- 0.05), procaine (pK'a = 8.11 +/- 0.04; log P = 1.10 +/- 0.08), and ephedrine (pK'a = 9.92 +/- 0.01; log P = 1.65 +/- 0.04) at 21 degrees C. PMID:16867718

  14. An added dimension: GC atmospheric pressure chemical ionization FTICR MS and the Athabasca oil sands.

    PubMed

    Barrow, Mark P; Peru, Kerry M; Headley, John V

    2014-08-19

    The Athabasca oil sands industry, an alternative source of petroleum, uses large quantities of water during processing of the oil sands. In keeping with Canadian environmental policy, the processed water cannot be released to natural waters and is thus retained on-site in large tailings ponds. There is an increasing need for further development of analytical methods for environmental monitoring. The following details the first example of the application of gas chromatography atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FTICR MS) for the study of environmental samples from the Athabasca region of Canada. APCI offers the advantages of reduced fragmentation compared to other ionization methods and is also more amenable to compounds that are inaccessible by electrospray ionization. The combination of GC with ultrahigh resolution mass spectrometry can improve the characterization of complex mixtures where components cannot be resolved by GC alone. This, in turn, affords the ability to monitor extracted ion chromatograms for components of the same nominal mass and isomers in the complex mixtures. The proof of concept work described here is based upon the characterization of one oil sands process water sample and two groundwater samples in the area of oil sands activity. Using the new method, the Ox and OxS compound classes predominated, with OxS classes being particularly relevant to the oil sands industry. The potential to resolve retention times for individual components within the complex mixture, highlighting contributions from isomers, and to characterize retention time profiles for homologous series is shown, in addition to the ability to follow profiles of double bond equivalents and carbon number for a compound class as a function of retention time. The method is shown to be well-suited for environmental forensics. PMID:25036898

  15. Picoelectrospray Ionization Mass Spectrometry Using Narrow-bore Chemically Etched Emitters

    SciTech Connect

    Marginean, Ioan; Tang, Keqi; Smith, Richard D.; Kelly, Ryan T.

    2014-01-01

    Electrospray ionization mass spectrometry (ESI-MS) at flow rates below ~10 nL/min has been only sporadically explored due to difficulty in reproducibly fabricating emitters that can operate at lower flow rates. Here we demonstrate narrow orifice chemically etched emitters for stable electrospray at flow rates as low as 400 pL/min. Depending on the analyte concentration, we observe two types of MS signal response as a function of flow rate. At low concentrations, an optimum flow rate is observed slightly above 1 nL/min, while the signal decreases monotonically with decreasing flow rates at higher concentrations. In spite of lower MS signal, the ion utilization efficiency increases exponentially with decreasing flow rate in all cases. No unimolecular response was observed within this flow rate range during the analysis of an equimolar mixture of peptides, indicating that ionization efficiency is an analyte-dependent characteristic in given experimental conditions. While little to no gain in signal-to-noise was achieved at ultralow flow rates for concentration-limited analyses, experiments consuming the same amount of analyte suggest that mass-limited analyses will benefit strongly from the use of low flow rates and avoiding unnecessary sample dilution. By operating under optimal conditions, consumption of just 500 zmol of sample yielded signal-to-noise ratios ~10 for some peptides. These findings have important implications for the analysis of trace biological samples.

  16. Soft ionization chemical analysis of secondary organic aerosol from green leaf volatiles emitted by turf grass.

    PubMed

    Jain, Shashank; Zahardis, James; Petrucci, Giuseppe A

    2014-05-01

    Globally, biogenic volatile organic compound (BVOC) emissions contribute 90% of the overall VOC emissions. Green leaf volatiles (GLVs) are an important component of plant-derived BVOCs, including cis-3-hexenylacetate (CHA) and cis-3-hexen-1-ol (HXL), which are emitted by cut grass. In this study we describe secondary organic aerosol (SOA) formation from the ozonolysis of dominant GLVs, their mixtures and grass clippings. Near-infrared laser desorption/ionization aerosol mass spectrometry (NIR-LDI-AMS) was used for chemical analysis of the aerosol. The chemical profile of SOA generated from grass clippings was correlated with that from chemical standards of CHA and HXL. We found that SOA derived from HXL most closely approximated SOA from turf grass, in spite of the approximately 5× lower emission rate of HXL as compared to CHA. Ozonolysis of HXL results in formation of low volatility, higher molecular weight compounds, such as oligomers, and formation of ester-type linkages. This is in contrast to CHA, where the hydroperoxide channel is the dominant oxidation pathway, as oligomer formation is inhibited by the acetate functionality. PMID:24666343

  17. Detection of alprazolam in hair by negative ion chemical ionization mass spectrometry

    Microsoft Academic Search

    Karin M. Höld; Dennis J. Crouch; Diana G. Wilkins; Douglas E. Rollins; Robert A. Maes

    1997-01-01

    A sensitive and specific method for the quantitative determination of alprazolam (AL) in hair has been developed. After the addition of deuterium labeled triazolam as an internal standard, hair samples (20 mg) were digested with 1 N NaOH at 40 °C overnight. Calibrators containing known concentrations of AL dried onto drug-free hair were also prepared and digested. After digestion, the

  18. Differeniation of Aroclors in environmental samples using negative ion chemical ionization (NICI) mass spectrometry

    SciTech Connect

    Ma, C.Y.; Bayne, C.K.; Maskarinec, M.P.

    1991-01-01

    Environmental samples suspected of containing polychlorinated biphenyls (PCB) and analyzed by EPA Method 8080 frequently contain non-PCB components, such as phthalates, PAH's, or organochlorine pesticides. The presence of these interferences can often obscure the GC/ECD patterns and cause problems in differentiating the Aroclor types by visual inspection. Since Method 8080 requires the identification of Aroclor types in order to trace the sources of PCB occurrences, NICI detection was used to provide additional parameters for discriminating PCB congeners from interferences. In this study, a pattern recognition method has been developed to classify the types of Aroclors for environmental samples. A computer program written in BASIC has been implemented to facilitate Aroclor classification using the NICI ion abundance measurement for PCB congeners. NICI measurements on Aroclor standards were used as training data set to develop classification methods for environmental samples. PCB contaminated oil or soil samples were either extracted of diluted with hexane and analyzed in the same manner as the standards. This sequential classification method classified all Aroclors in the training set correctly. A set of 15 environmental samples with known Aroclor types were also correctly classified.

  19. Water chemical ionization mass spectrometry of aldehydes, ketones esters, and carboxylic acids

    SciTech Connect

    Hawthorne, S.B.; Miller, D.J.

    1986-11-01

    Chemical ionization mass spectrometry (CI) of aliphatic and aromatic carbonyl compounds using water as the reagent gas provides intense pseudomolecular ions and class-specific fragmentation patterns that can be used to identify aliphatic aldehydes, ketones, carboxylic acids, and esters. The length of ester acyl and alkyl groups can easily be determined on the basis of loss of alcohols from the protonated parent. Water CI provides for an approximately 200:1 selectivity of carbonyl species over alkanes. No reagent ions are detected above 55 amu, allowing species as small as acetone, propanal, acetic acid, and methyl formate to be identified. When deuterate water was used as the reagent, only the carboxylic acids and ..beta..-diketones showed significant H/D exchange. The use of water CI to identify carbonyl compounds in a wastewater from the supercritical water extraction of lignite coal, in lemon oil, and in whiskey volatiles is discussed.

  20. Demonstration of real-time monitoring of a photolithographic exposure process using chemical ionization mass spectrometry

    SciTech Connect

    Mowry, C.D. [Sandia National Labs., Albuquerque, NM (United States). Analytical Chemistry Dept.

    1998-02-01

    Silicon wafers are coated with photoresist and exposed to ultraviolet (UV) light in a laboratory to simulate typical conditions expected in an actual semiconductor manufacturing process tool. Air is drawn through the exposure chamber and analyzed using chemical ionization mass spectrometry (CI/MS). Species that evaporate or outgas from the wafer are thus detected. The purpose of such analyses is to determine the potential of CI/MS as a real-time process monitoring tool. Results demonstrate that CI/MS can remotely detect the products evolved before, during, and after wafer UV exposure; and that the quantity and type of products vary with the photoresist coated on the wafer. Such monitoring could provide semiconductor manufacturers benefits in quality control and process analysis. Tool and photoresist manufacturers could also realize benefits from this measurement technique with respect to new tool, method, or photoresist development. The benefits realized can lead to improved device yields and reduced product and development costs.

  1. Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry for Identification of Nonfermenting Gram-Negative Bacilli Isolated from Cystic Fibrosis Patients

    Microsoft Academic Search

    Nicolas Degand; Etienne Carbonnelle; Brunhilde Dauphin; Jean-Luc Beretti; Muriel Le Bourgeois; Isabelle Sermet-Gaudelus; Christine Segonds; Patrick Berche; Xavier Nassif; Agnes Ferroni; UniversiteParis Descartes; Service de Pediatrie Generale

    2008-01-01

    The identification of nonfermenting gram-negative bacilli isolated from cystic fibrosis (CF) patients is usually achieved by using phenotype-based techniques and eventually molecular tools. These techniques remain time-consuming, expensive, and technically demanding. We used a method based on matrix- assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF-MS) for the identi- fication of these bacteria. A set of reference strains belonging

  2. Comparison of the binding stoichiometries of positively charged DNA-binding drugs using positive and negative ion electrospray ionization mass spectrometry

    Microsoft Academic Search

    Rajesh Gupta; Jennifer L. Beck; Stephen F. Ralph; Margaret M. Sheil; Janice R. Aldrich-Wright

    2004-01-01

    Positive and negative ion electrospray ionization (ESI) mass spectra of complexes of positively charged small molecules (distamycin,\\u000a Hoechst 33258, [Ru(phen)2dpq]Cl2 and [Ru(phen)2dpqC]Cl2) have been compared. [Ru(phen)2dpq]Cl2 and [Ru(phen)2dpqC]Cl2 bind to DNA by intercalation. Negative ion ESI mass spectra of mixtures of [Ru(phen)2dpq]Cl2 or [Ru(phen)2dpqC]Cl2 with DNA showed ions from DNA-ligand complexes consistent with solution studies. In contrast, only ions from

  3. Hop as an interesting source of resveratrol for brewers: optimization of the extraction and quantitative study by liquid chromatography/atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

    Callemien, Delphine; Jerkovic, Vesna; Rozenberg, Raoul; Collin, Sonia

    2005-01-26

    Nowadays, hop is used almost exclusively by brewers for bitterness and flavor. Although hop polyphenols have been widely studied in the past decade for their antioxidant activity in the boiling kettle, very little is known about their real impact on health. The discovery of resveratrol in hop pellets highlights the potential health-promoting effect of moderate beer consumption. Here, we have optimized a quantitative extraction procedure for resveratrol in hop pellets. Preliminary removal of hydrophobic bitter compounds with toluene and cyclohexane at room temperature allows 99% trans-resveratrol recovery by ethanol:water (75:25, v/v) solid/liquid extraction at 60 degrees C. Reverse phase liquid chromatography proves an excellent means of separating isomers. In addition, we have compared two mass spectrometry ionization methods-atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI)-in both the positive and the negative modes. On the basis of standard additions applied with the optimized extraction procedure and reverse phase high-performance liquid chromatography-APCI(+)-tandem mass spectrometry, it appears that Tomahawk hop pellets (T90, harvest 2002) contain 0.5 ppm trans-resveratrol, 2 ppm trans-piceid, no cis-resveratrol, and 0.9 ppm cis-piceid. PMID:15656683

  4. Facilities: NHMFL 9.4 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer Citation: Atmospheric Pressure Laser-Induced Acoustic Desorption Chemical Ionization Mass Spectrometry

    E-print Network

    Weston, Ken

    : Atmospheric Pressure Laser-Induced Acoustic Desorption Chemical Ionization Mass Spectrometry for Analysis of atmospheric pressure laser-induced acoustic desorption chemical ionization (AP/ LIAD-CI) source. The laser a powerful new approach for the analysis of saturated hydrocarbon mixtures: atmospheric pressure laser

  5. Self-Aspirated Atmospheric Pressure Chemical Ionization Source for Direct Sampling of Analytes on Surfaces and in Liquid Solutions

    Microsoft Academic Search

    Keiji G. Asano; Michael J. Ford; Bruce A. Tomkins; Gary J. Van Berkel

    2005-01-01

    A self-aspirating heated nebulizer probe is described and demonstrated for use in the direct analysis of analytes on surfaces and in liquid samples by atmospheric pressure chemical ionization (APCI) mass spectrometry. Functionality and performance of the probe as a self-aspirating APCI source is demonstrated using reserpine and progesterone as test compounds. The utility of the probe to sample analytes directly

  6. Capillary liquid chromatography-microchip atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Ostman, Pekka; Jäntti, Sirkku; Grigoras, Kestas; Saarela, Ville; Ketola, Raimo A; Franssila, Sami; Kotiaho, Tapio; Kostiainen, Risto

    2006-07-01

    A miniaturized nebulizer chip for capillary liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (capillary LC-microchip APCI-MS) is presented. The APCI chip consists of two wafers, a silicon wafer and a Pyrex glass wafer. The silicon wafer has a DRIE etched through-wafer nebulizer gas inlet, an edge capillary insertion channel, a stopper, a vaporizer channel and a nozzle. The platinum heater electrode and pads for electrical connection were patterned on to the Pyrex glass wafer. The two wafers were joined by anodic bonding, creating a microchip version of an APCI-source. The sample inlet capillary from an LC column is directly connected to the vaporizer channel of the APCI chip. The etched nozzle in the microchip forms a narrow sample plume, which is ionized by an external corona needle, and the formed ions are analyzed by a mass spectrometer. The nebulizer chip enables for the first time the use of low flow rate separation techniques with APCI-MS. The performance of capillary LC-microchip APCI-MS was tested with selected neurosteroids. The capillary LC-microchip APCI-MS provides quantitative repeatability and good linearity. The limits of detection (LOD) with a signal-to-noise ratio (S/N) of 3 in MS/MS mode for the selected neurosteroids were 20-1000 fmol (10-500 nmol l(-1)). LODs (S/N = 3) with commercial macro APCI with the same compounds using the same MS were about 10 times higher. Fast heat transfer allows the use of the optimized temperature for each compound during an LC run. The microchip APCI-source provides a convenient and easy method to combine capillary LC to any API-MS equipped with an APCI source. The advantages and potentials of the microchip APCI also make it a very attractive interface in microfluidic APCI-MS. PMID:16804601

  7. The role of different phenomena in surface-activated chemical ionization (SACI) performance.

    PubMed

    Cristoni, Simone; Bernardi, Luigi Rossi; Guidugli, Federico; Tubaro, Michela; Traldi, Pietro

    2005-12-01

    In previous studies, the production of ions in an APCI source without any corona discharge was observed, and the intensity of the ion signals showed significant increases on placing a metallic surface at 45 degrees inside an orthogonal ion source. This method was named surface-activated chemical ionization (SACI). The present study was performed to investigate the mechanisms of ion production with or without the presence of the metallic surface, by varying instrumental parameters and the geometrical configuration. Approximate calculations show that, in the absence of corona discharge and of any additional surfaces, ions cannot be produced by collisional phenomena, because of their low kinetic energy, in the 10(-2) to 10(-3) eV range. Two alternative possibilities have been considered: the first takes into account that ions may originate by collision of neutral clusters of polar solvent molecules with the APCI source surfaces through clusterelectric effect. The second takes into account that the water dissociation constant k(w) is temperature dependent, passing from 10(-14.1669) at 20 degrees C to 10(-12.4318) at 90 degrees C. It means that the [H(+)] varies from 8.3 x 10(-8) to 6.1 x 10(-7) M going from 20 to 90 degrees C. Hence, at the high temperatures experimented in the APCI vaporizer, H(+) becomes available in solution in molar quantities analogous to those of analyte, and the protonation of the analyte itself can consequently occur. The activation of further ionization processes in the presence of the metallic surface can be reasonably attributed to interactions between gas-phase analyte molecules and solvent molecules adsorbed on the surface. Experiments performed with a thin layer of deuterated glycerol on the surface led to unequivocal results, i.e. the production of [M + D](+) ions of the analyte. PMID:16320302

  8. Alternately Pulsed Nano-electrospray Ionization/Atmospheric Pressure Chemical Ionization for Ion/Ion Reactions in an Electrodynamic Ion Trap

    PubMed Central

    Liang, Xiaorong; Xia, Yu; McLuckey, Scott A.

    2008-01-01

    The alternate operation of nano-electrospray ionization (nano-ESI) and atmospheric pressure chemical ionization (APCI), using a common atmosphere/vacuum interface and ion path, has been implemented to facilitate ion/ion reaction experiments in a linear ion trap-based tandem mass spectrometer. The ion sources are operated in opposite polarity modes whereby one of the ion sources is used to form analyte ions while the other is used to form reagent ions of opposite polarity. This combination of ion sources is well-suited to implementation of experiments involving multiply charged ions in reaction with singly charged ions of opposite polarity. Three analytically useful ion/ion reactions types are illustrated: the partial deprotonation of a multiply protonated protein, the partial protonation of a multiply deprotonated oligonucleotide, and electron transfer to a multiply protonated peptide. The approach described herein is attractive in that it enables both single proton transfer and single electron transfer ion/ion reaction experiments to be implemented without requiring major modifications to the tandem mass spectrometer hardware. Furthermore, a wide range of reactant ions can be formed with these ionization methods and the pulsed nature of operation appears to lead to no significant compromise in the performance of either ion source. PMID:16643016

  9. Determination of nivalenol and deoxynivalenol in wheat using liquid chromatography–mass spectrometry with negative ion atmospheric pressure chemical ionisation

    Microsoft Academic Search

    E Razzazi-Fazeli; J Böhm; W Luf

    1999-01-01

    A new, rapid and sensitive method has been developed for the determination of nivalenol (NIV) and deoxynivalenol (DON) by using HPLC in combination with an atmospheric pressure chemical ionization (APCI)-interface and a single quadrupole mass spectrometer. Different LC and MS parameters have been optimized prior to this in order to obtain better results and sensitivity. The effect of nebulizing temperature

  10. Herbert P. Broida Prize Lecture: Probing chemical dynamics with negative ion photodetachment

    NASA Astrophysics Data System (ADS)

    Neumark, Daniel

    2013-03-01

    Photoelectron spectroscopy and its variants have been used in our laboratory to study diverse phenomena in chemical dynamics, including transition state spectroscopy, the electronic and vibrational spectroscopy of clusters, the photodissociation of reactive free radicals, hydrated electron dynamics in clusters and liquid jets, and the ultrafast dynamics of helium nanodroplets. This talk will focus on two examples of this type of work: slow electron velocity map imaging (SEVI) of trapped and cooled negative ions, and time-resolved photoelectron spectroscopy (TRPES) of negative ions. SEVI of cold ions represents a powerful means of performing high resolution photoelectron spectroscopy on complex species. Time-resolved radiation chemistry in nucleobases will be carried out with TRPES. In this work, starting with iodide-nucleobase complexes, we inject electrons into low-lying unoccupied orbitals of the nucleobase and follow the ensuing dynamics.

  11. Direct quantification of chemical warfare agents and related compounds at low ppt levels: comparing active capillary dielectric barrier discharge plasma ionization and secondary electrospray ionization mass spectrometry.

    PubMed

    Wolf, Jan-Christoph; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

    2015-01-01

    A novel active capillary dielectric barrier discharge plasma ionization (DBDI) technique for mass spectrometry is applied to the direct detection of 13 chemical warfare related compounds, including sarin, and compared to secondary electrospray ionization (SESI) in terms of selectivity and sensitivity. The investigated compounds include an intact chemical warfare agent and structurally related molecules, hydrolysis products and/or precursors of highly toxic nerve agents (G-series, V-series, and "new" nerve agents), and blistering and incapacitating warfare agents. Well-defined analyte gas phase concentrations were generated by a pressure-assisted nanospray with consecutive thermal evaporation and dilution. Identification was achieved by selected reaction monitoring (SRM). The most abundant fragment ion intensity of each compound was used for quantification. For DBDI and SESI, absolute gas phase detection limits in the low ppt range (in MS/MS mode) were achieved for all compounds investigated. Although the sensitivity of both methods was comparable, the active capillary DBDI sensitivity was found to be dependent on the applied AC voltage, thus enabling direct tuning of the sensitivity and the in-source fragmentation, which may become a key feature in terms of field applicability. Our findings underline the applicability of DBDI and SESI for the direct, sensitive detection and quantification of several CWA types and their degradation products. Furthermore, they suggest the use of DBDI in combination with hand-held instruments for CWAs on-site monitoring. PMID:25427190

  12. Bake condition effect on hybrid lithography process for negative-tone chemically amplified resists

    NASA Astrophysics Data System (ADS)

    Pain, Laurent; Sala, F.; Higgins, C.; Dal'zotto, B.; Tedesco, Serge V.

    2000-06-01

    This paper presents the process optimization study of negative tone Chemically Amplified Resists (CAR) under E-Beam exposure. The importance of post apply bake temperature choice on resolution is underlined. The process study determines the process window in which optimal conditions of both post apply and post exposure bake steps are defined and present a method to define more precisely the thermal cross-linking onset. Finally lithographic performances of CARs are studied and we show that resolution can be pushed down to 40 nm.

  13. Differentiation of glucose-containing disaccharides isomers by fragmentation of the deprotonated non-covalent dimers using negative electrospray ionization tandem mass spectrometry.

    PubMed

    Wan, Debin; Yang, Hongmei; Yan, Cunyu; Song, Fengrui; Liu, Zhiqiang; Liu, Shuying

    2013-10-15

    In this work, the glucose-containing disaccharide isomers were studied using negative electrospray ionization tandem mass spectrometry (ESI-MS/MS). Interestingly, the full-scan mass spectra of the disaccharides revealed that the deprotonated dimers were the predominant gas phase ions during ionization process. Importantly, several diagnostic fragment ions relative to linkage positions and anomeric configurations, arising from the covalent bond dissociation of dimers without breakdown of the non-covalent complexes, can be detected in the tandem mass spectra. Based on the scarce fragmentation characteristic, an original and simple approach for structural discrimination of disaccharide isomers was put forward. In addition, density functional theory (DFT) was employed to find out the reason why several fragmentations of intramolecular sugar bonds had preceded breakdown of the non-covalent complexes. PMID:24054676

  14. Modeling the Charging of Highly Oxidized Cyclohexene Ozonolysis Products Using Nitrate-Based Chemical Ionization.

    PubMed

    Hyttinen, Noora; Kupiainen-Määttä, Oona; Rissanen, Matti P; Muuronen, Mikko; Ehn, Mikael; Kurtén, Theo

    2015-06-18

    Several extremely low volatility organic compounds (ELVOCs) formed in the ozonolysis of endocyclic alkenes have recently been detected in laboratory and field studies. These experiments have been carried out with chemical ionization atmospheric pressure interface time-of-flight mass spectrometers (CI-APi-TOF) with nitrate ions as reagent ions. The nitrate ion binds to the detected species through hydrogen bonds, but it also binds very strongly to one or two neutral nitric acid molecules. This makes the measurement highly selective when there is an excess amount of neutral nitric acid in the instrument. In this work, we used quantum-chemical methods to calculate the binding energies between a nitrate ion and several highly oxidized ozonolysis products of cyclohexene. These were then compared with the binding energies of nitrate ion-nitric acid clusters. Systematic configurational sampling of the molecules and clusters was carried out at the B3LYP/6-31+G* and ?B97xD/aug-cc-pVTZ levels, and the final single-point energies were calculated with DLPNO-CCSD(T)/def2-QZVPP. The binding energies were used in a kinetic simulation of the measurement system to determine the relative ratios of the detected signals. Our results indicate that at least two hydrogen bond donor functional groups (in this case, hydroperoxide, OOH) are needed for an ELVOC molecule to be detected in a nitrate ion CI-APi-TOF. Also, a double bond in the carbon backbone makes the nitrate cluster formation less favorable. PMID:26023711

  15. A chemical ionization mass spectrometry technique for airborne measurements of ammonia

    NASA Astrophysics Data System (ADS)

    Nowak, J. B.; Neuman, J. A.; Kozai, K.; Huey, L. G.; Tanner, D. J.; Holloway, J. S.; Ryerson, T. B.; Frost, G. J.; McKeen, S. A.; Fehsenfeld, F. C.

    2007-05-01

    A chemical ionization mass spectrometer (CIMS) utilizing protonated acetone dimer ion chemistry to measure gas-phase ammonia (NH3) from the NOAA WP-3D aircraft is described. The average sensitivity determined from in-flight standard addition calibrations ranged from 2.6 to 5 ion counts s-1 pptv-1, depending on flow conditions, for 1 MHz of reagent ion signal. The instrument time response was determined to be 5 s from the 2 e-folding signal decay time after removal of a standard addition calibration. The instrumental background varied from flight to flight ranging from 0.5 to 1.3 ppbv. The variability between successive background measurements ranged from 50 pptv to 100 pptv. Total uncertainty for the 5 s data was conservatively estimated to be ±(30% + 125 pptv). Two NH3 sources were sampled during the New England Air Quality Study-Intercontinental Transport and Chemical Transformation (NEAQS-ITCT) 2004 campaign, one urban and one agricultural. During the 25 July flight, enhancements in NH3 mixing ratios were coincident with enhancements in CO, NOx, and SO2 mixing ratios downwind of New York City. The NH3 mixing ratios in the urban outflow plume ranged from 0.4 to 1 ppbv, or enhancements of 0.2 to 0.8 ppbv above local background. During the 15 August flight, NH3 mixing ratios were enhanced 0.3 to 0.45 ppbv above local background directly downwind of an agricultural area northeast of Atlanta, Georgia. The NH3 CIMS instrument has shown the ability to measure sub-ppbv NH3 levels at high time resolution from an aircraft.

  16. Unusual atmospheric pressure chemical ionization conditions for detection of organic peroxides.

    PubMed

    Rondeau, David; Vogel, René; Tabet, Jean-Claude

    2003-09-01

    Organic peroxides such as the cumene hydroperoxide I (M(r) = 152 u), the di-tert-butyl peroxide II (M(r) = 146 u) and the tert-butyl peroxybenzoate III (M(r) = 194 u) were analyzed by atmospheric pressure chemical ionization mass spectrometry using a water-methanol mixture as solvent with a low flow-rate of mobile phase and unusual conditions of the source temperature (< or =50 degrees C) and probe temperature (70-200 degrees C). The mass spectra of these compounds show the formation of (i) an [M + H](+) ion (m/z 153) for the hydroperoxide I, (ii) a stable adduct [M + CH(3)OH(2)](+) ion (m/z 179) for the dialkyl peroxide II and (iii) several protonated adduct species such as protonated molecules (m/z 195) and different protonated adduct ions (m/z 227, 389 and 421) for the peroxyester III. Tandem mass spectrometric experiments, exact mass measurements and theoretical calculations were performed for characterize these gas-phase ionic species. Using the double-well energy potential model illustrating a gas-phase bimolecular reaction, three important factors are taken into account to propose a qualitative interpretation of peroxide behavior toward the CH(3)OH(2) (+), i.e. thermochemical parameters (DeltaHdegrees(reaction)) and two kinetic factors such as the capture constant of the initial stable ion-dipole and the magnitude of the rate constant of proton transfer reaction into the loose proton bond cluster. PMID:14505320

  17. Performance of a corona ion source for measurement of sulfuric acid by chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kürten, A.; Rondo, L.; Ehrhart, S.; Curtius, J.

    2011-03-01

    The performance of an ion source based on corona discharge has been studied. This source is used for the detection of gaseous sulfuric acid by chemical ionization mass spectrometry (CIMS) through the reaction of NO3- ions with H2SO4. The ion source is operated under atmospheric pressure and its design is similar to the one of a radioactive (americium-241) ion source which has been used previously. The results show that the detection limit for the corona ion source is sufficiently good for most applications. For an integration time of 1 min it is ~6 × 104 molecule cm-3 of H2SO4. In addition, only a small cross-sensitivity to SO2 has been observed for concentrations as high as 1 ppmv in the sample gas. This low sensitivity to SO2 is achieved even without the addition of an OH scavenger. When comparing the new corona ion source with the americium ion source for the same provided H2SO4 concentration, both ion sources yield almost identical values. These features make the corona ion source investigated here favorable over the more commonly used radioactive ion sources for most applications where H2SO4 is measured by CIMS.

  18. Atmospheric pressure chemical ionization of explosives using alternating current corona discharge ion source.

    PubMed

    Usmanov, D T; Chen, L C; Yu, Z; Yamabe, S; Sakaki, S; Hiraoka, K

    2015-04-01

    The high-sensitive detection of explosives is of great importance for social security and safety. In this work, the ion source for atmospheric pressure chemical ionization/mass spectrometry using alternating current corona discharge was newly designed for the analysis of explosives. An electromolded fine capillary with 115?µm inner diameter and 12?mm long was used for the inlet of the mass spectrometer. The flow rate of air through this capillary was 41?ml/min. Stable corona discharge could be maintained with the position of the discharge needle tip as close as 1?mm to the inlet capillary without causing the arc discharge. Explosives dissolved in 0.5?µl methanol were injected to the ion source. The limits of detection for five explosives with 50?pg or lower were achieved. In the ion/molecule reactions of trinitrotoluene (TNT), the discharge products of NOx (-) (x?=?2,3), O3 and HNO3 originating from plasma-excited air were suggested to contribute to the formation of [TNT?-?H](-) (m/z 226), [TNT?-?NO](-) (m/z 197) and [TNT?-?NO?+?HNO3 ](-) (m/z 260), respectively. Formation processes of these ions were traced by density functional theory calculations. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26149109

  19. Characterization of complex assemblages of organic acids in geological samples by negative electrospray ionization mass spectrometry using a double-focusing magnetic sector field mass spectrometer.

    PubMed

    Pötz, Stefanie; Wilkes, Heinz; Witt, Matthias; Horsfield, Brian

    2010-04-30

    Four different geological sample types (a crude oil, a crude oil asphaltene, a reservoir core extract and a reservoir core asphaltene) have been characterized by negative ionization electrospray mass spectrometry at low and high mass resolution using a double-focusing magnetic sector field mass spectrometer. The mass range, shape of the spectra and the signal distribution of the acidic constituents as well as the average molecular weights, the total ion abundance and signal intensity in the spectra were compared for the different sample types. Nominal mass classes have been evaluated and Kendrick mass plots were generated in order to identify homologous series. For the crude oil sample, accurate mass assignments were made by high-resolution double-focusing magnetic sector field mass spectrometry (DFMSFMS) and were compared with those obtained by negative ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). With both instrument types, compounds with the molecular composition C(n)H(2n+z)O(2), among which carboxylic acids predominated, were the main acidic compound class detectable in negative ESI mass spectra. Good agreement was achieved for the double bond class distribution and the carbon number distribution of the O(2) class. In addition, minor compound classes could be identified using FTICRMS. PMID:20301135

  20. Ionization mechanism of the ambient pressure pyroelectric ion source (APPIS) and its applications to chemical nerve agent detection.

    PubMed

    Neidholdt, Evan L; Beauchamp, J L

    2009-11-01

    We present studies of the ionization mechanism operative in the ambient pressure pyroelectric ionization source (APPIS), along with applications that include detection of simulants for chemical nerve agents. It is found that ionization by APPIS occurs in the gas-phase. As the crystal is thermally cycled over a narrow temperature range, electrical discharges near the surface of the crystal produce energetic species which, through reactions with atmospheric molecules, result in reactant ions such as protonated water clusters or clusters of hydroxide and water. Reactant ions can be observed directly in the mass spectrometer. These go on to react with trace neutrals via proton transfer reactions to produce the ions observed in mass spectra, which are usually singly protonated or deprotonated species. Further implicating gas-phase ionization, observed product distributions are highly dependent on the composition of ambient gases, especially the concentration of water vapor and oxygen surrounding the source. For example, basic species such as triethylamine are observed as singly protonated cations at a water partial pressure of 10 torr. At a water pressure of 4 torr, reactive oxygen species are formed and lead to observation of protonated amine oxides. The ability of the APPIS source to detect basic molecules with high proton affinities makes it highly suited for the detection of chemical nerve agents. We demonstrate this application using simulants corresponding to VX and GA (Tabun). With the present source configuration pyridine is detected readily at a concentration of 4 ppm, indicating ultimate sensitivity in the high ppb range. PMID:19682922

  1. We highlight the selective ionization of acidic components of crude oils and naphthenates by negative-ion electrospray

    E-print Network

    We highlight the selective ionization of acidic components of crude oils and naphthenates and naphthenic acids in petroleum without derivatization or preconcentration of the sample, and with minimal differences of acidic species in crude oils and naphthenates and also afford structural characterization

  2. Engelking, Lineberger PES of the Negative Ions of Iron and Iron Carbonyls 5569 30, 850 (1973)) in the two ionized states involving the ionization of 3s

    E-print Network

    Lineberger, W. Carl

    1973-01-01

    for the Series Fe(CO),, n = 0, 1, 2, 3, 4 P. C. Engelking? and W. C. Lineberger* Contributionfrom the Department-frequency Ar ion laser, the photoelectron spectra of the negative ions Fe-, FeCO-, Fe(CO)r-, Fe- (CO)3-, and Fe the electron affinities for other members of this series increase roughly as the number of ligands. Thus for FeCO

  3. Sodium trifluoroacetate as a tune\\/calibration compound for positive- and negative-ion electrospray ionization mass spectrometry in the mass range of 100–4000 Da

    Microsoft Academic Search

    Mehdi Moini; Bruce L. Jones; Robin M. Rogers; Longfei Jiang

    1998-01-01

    We have identified aqueous:acetonitrile solutions of alkali-metal trifluoroacetate compounds as tune\\/calibration standards\\u000a for both positive- and negative-ion electrospray ionization mass spectrometry (ESI\\/MS). Each alkali-metal trifluoroacetate\\u000a solution in water and acetonitrile (50:50, v\\/v) yields evenly spaced, singly charged peaks in the mass range of 100–3500 Da.\\u000a Intense peaks are formed either by infusing the solution using a syringe pump, by infusing

  4. Stability studies of propoxur herbicide in environmental water samples by liquid chromatography–atmospheric pressure chemical ionization ion-trap mass spectrometry

    Microsoft Academic Search

    Lei Sun; Hian Kee Lee

    2003-01-01

    Liquid chromatography–atmospheric pressure ionization ion-trap mass spectrometry has been investigated for the analysis of polar pesticides in water. The degradation behavior of propoxur, selected as a model pesticide belonging to the N-methylcarbamate group, in various aqueous matrices (Milli-Q water, drinking water, rain water, seawater and river water) was investigated. Two interfaces of atmospheric pressure ionization, atmospheric pressure chemical ionization (APCI)

  5. Determination of nivalenol and deoxynivalenol in wheat using liquid chromatography-mass spectrometry with negative ion atmospheric pressure chemical ionisation.

    PubMed

    Razzazi-Fazeli, E; Böhm, J; Luf, W

    1999-08-27

    A new, rapid and sensitive method has been developed for the determination of nivalenol (NIV) and deoxynivalenol (DON) by using HPLC in combination with an atmospheric pressure chemical ionization (APCI)-interface and a single quadrupole mass spectrometer. Different LC and MS parameters have been optimized prior to this in order to obtain better results and sensitivity. The effect of nebulizing temperature on the sensitivity and fragmentation of NIV and DON in an APCI interface was investigated. Also, the influence of the cone voltage on the fragmentation pattern was studied, which was shown to have a tremendous effect. Furthermore, the effect of modifiers such as ammonium acetate, acetic acid and ammonia on the ionisation yield of the above substances have been investigated. The extraction was carried out using acetonitrile-water. A two step purification was then applied on two different Mycosep clean up columns. We have used a modified, rapid and isocratic HPLC method combined with a negative ion APCI-MS for the separation and quantitative determination of NIV and DON in wheat extract. An RP C18 column was used for the separation of selected compounds in wheat extract with water-acetonitrile-methanol (82:9:9, v/v/v) at a flow-rate of 1 ml/min without a split. Calibration curves show good linearity and reproducibility. The detection limit and precision were determined for NIV and DON. Both compounds could be detected down to microg/kg level in wheat using selected ion monitoring of the [M-H]- ions and the main fragments. PMID:10497927

  6. Chemical Characterization of Crude Petroleum Using Nanospray Desorption Electrospray Ionization Coupled with High-Resolution Mass Spectrometry

    SciTech Connect

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

    2012-02-07

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

  7. Rapid screening procedures for the hydrolysis products of chemical warfare agents using positive and negative ion liquid chromatography–mass spectrometry with atmospheric pressure chemical ionisation

    Microsoft Academic Search

    Robert W Read; Robin M Black

    1999-01-01

    Qualitative screening procedures have been developed for the rapid detection and identification of the hydrolysis products of chemical warfare agents in aqueous samples and extracts, using liquid chromatography–mass spectrometry with positive and negative atmospheric pressure chemical ionisation (APCI). Previously reported screening procedures, which used positive APCI or electrospray ionisation (ESI), were modified by using LC conditions that allowed acquisition of

  8. Transport behavior and negative magnetoresistance in chemically reduced graphene oxide nanofilms

    NASA Astrophysics Data System (ADS)

    Wang, Shu-Wei; Lin, H. E.; Lin, Huang-De; Chen, K. Y.; Tu, Kun-Hua; Chen, C. W.; Chen, Ju-Ying; Liu, Cheng-Hua; Liang, C.-T.; Chen, Y. F.

    2011-08-01

    The electron transport behavior in chemically reduced graphene oxide (rGO) sheets with different thicknesses of 2, 3, and 5 nm was investigated. The four-probe method for the sheet resistance (RS) measurement on the intensively reduced graphene oxide samples indicates an Arrhenius characteristic of the electron transport at zero magnetic field B = 0, consistent with previous experimental results on well-reduced GO samples. The anticipated variable range hopping (VRH) transport of electrons in a two-dimensional electron system at low temperatures was not observed. The measured RS of the rGO samples are below 52 k?/square at room temperature. With the application of a magnetic field up to 4 T, negative magnetoresistance in the Mott VRH regime was observed. The magnetotransport features support a model based on the spin-coupling effect from the vacancy-induced midgap states that facilitate the Mott VRH conduction in the presence of an external magnetic field.

  9. The Effect of the Ionization Rate on the Chemical Composition of Dense Cores of Dark Molecular Clouds

    NASA Astrophysics Data System (ADS)

    Kirsanova, M. S.; Wiebe, D. S.

    2004-09-01

    The effect of variations in the rate of ionization of neutral chemical species by cosmic rays, ?, on the abundances of some observed molecules in the dense cores of dark molecular clouds is studied. Changes in molecular abundances accompanying an increased (decreased) ionization rate have a single origin: the acceleration (deceleration) of processes that are affected directly or indirectlybychemical reactions with charged species. In addition to affecting the gas-phase chemistry, an increased cosmic-ray flux leads to the more efficient destruction of dust-grain mantles and also accelerates the freezing of some components onto dust. In particular, in a model with an increased ?, the destruction of the volatile N2 molecule by ionized helium leads to the rapid accumulation of nitrogen atoms in dust-phase ammonia, which has a higher desorption energythan N2. As a result, the gas-phase abundance of NH3 and N2H+ decreases significantly. This mechanism can explain the unusual chemical structures of some dense globules, such as B68, where surprisingly low abundances of nitrogen-bearing molecules are observed together with a central drop in the NH3 and N2H+ column densities. Observations of clouds in HCN and HNC lines can discriminate between the two possible origins of the reduced NH3 and N2H+ abundances: an increased cosmic-ray flux or N2 freezing due to the higher desorption energy of this molecule.

  10. Identification of ubiquinones and menaquinones in activated sludge by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Gao, Meng-chun; Yang, Min; Hu, Jian-ying; Shao, Bing; Zhang, Hai-feng; Li, Hong-yan

    2003-07-25

    A sensitive analytical method has been developed for identification of ubiquinones (UQ-n(Hx)) and menaquinones (MK-n(Hx)) in activated sludge by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry in negative mode (LC-NI-APCI-MS). Extraction and clean-up of samples were carried out on Sep-Pak Plus Silica solid-phase extraction cartridges. Complete separation of quinones was achieved with an ODS analytical column and using isopropyl ether-methanol (17:83, v/v) as the mobile phase. The compositions of ubiquinones and menaquinones were determined directly using combined information on retention time, the molecular ion mass and fragment ion masses. The lowest instrument quantitative detection limits (LODinst) for UQ-6, UQ-10, and Vitamin K1 were estimated to be 0.4, 4 and 0.12 ng (S/N = 10) using LC-NI-APCI-MS in SIM mode, and the lowest method detection limits (LODmeth) achieved by spiking experiment were estimated to be 0.2, 2 and 0.06 microg/g for UQ-6, UQ-10 and Vitamin K1, respectively. On the other hand, the LODinst for UQ-6, UQ-10, and Vitamin K1 were estimated to be 10, 100 and 2 ng (S/N = 10) using LC-NI-APCI-MS in full-scan mode, and the LODmeth were estimated to be 7, 60 and 1.2 microg/g for UQ-6, UQ-10, and Vitamin K1, respectively. Both LC-NI-APCI-MS and LC-UV/DAD were applied in the analysis of an activated sludge extract. UQ-n (n = 6-10), MK-n (n = 6-10), MK-n(H2) (n = 7-10), MK-n(H4) (n = 8-9) and MK-8(H6) were detected by LC-NI-APCI-MS, while UQ-6, UQ-7, MK-7(H), MK-9 and MK-10(H2) were not found by LC-UV/DAD. These results suggest that LC-NI-APCI-MS is more sensitive than LC-UV/DAD for the analysis of quinones in environmental samples such as sediment, activated sludge and bio-film in biological processes and other aquatic environments. PMID:12924548

  11. Photodetachment of negative helium ions below and above the 1s ionization threshold: A complex scaled configuration-interaction approach

    SciTech Connect

    Sanz-Vicario, Jose Luis; Lindroth, Eva; Brandefelt, Nicklas [Department of Atomic Physics, Stockholms Centrum foer Fysik, Astronomi och Bioteknik (SCFAB), Fysikum, S-106 91 Stockholm (Sweden)

    2002-11-01

    The photodetachment of the metastable He{sup -} 1s2s2p {sup 4}P{sup o} state has been calculated in two photon energy regions of interest: the first, named here as energy region I, below the double photoionization threshold He{sup +}(n=1), involving outer-shell ionization and doubly excited states of He{sup -}, and the second, named here as region II, above the He{sup -} 1s ionization threshold and below the He{sup +}(n=2) threshold, involving K-shell detachment and triply excited states of a He{sup -} ''hollow ion.'' We have implemented an ab initio three-electron configuration-interaction method in the LS-coupling scheme combined with complex scaling to obtain resonance positions and widths and the photodetachment cross sections. We have revisited region I, although widely studied before, as a test of our method. Notwithstanding some small discrepancies, our complex scaling results compare well with the previously published results and also add new understanding to some features in the cross section. Our emphasis is given to K-shell photodetachment in photon energy region II, where comparison is made with two other recent theoretical calculations that use completely different methods, and that were in dispute. We also compare with a very recent experiment for the He{sup -} K-shell photodetachment, which displays three major features; a broad nonresonant hump after the He 2s2p {sup 3}P{sup o} threshold and two other peaks. A complex scaling analysis of prominent structures in the photodetachment spectra in region II, previously claimed to be nonresonant structures, leads to a different conclusion; i.e., they are all true triply excited-state resonances, and two of them correspond to the peaks observed experimentally.

  12. High-resolution chemical depth profiling of solid material using a miniature laser ablation/ionization mass spectrometer.

    PubMed

    Grimaudo, Valentine; Moreno-García, Pavel; Riedo, Andreas; Neuland, Maike B; Tulej, Marek; Broekmann, Peter; Wurz, Peter

    2015-02-17

    High-resolution chemical depth profiling measurements of copper films are presented. The 10 ?m thick copper test samples were electrodeposited on a Si-supported Cu seed under galvanostatic conditions in the presence of particular plating additives (SPS, Imep, PEI, and PAG) used in the semiconductor industry for the on-chip metallization of interconnects. To probe the trend of these plating additives toward inclusion into the deposit upon growth, quantitative elemental mass spectrometric measurements at trace level concentration were conducted by using a sensitive miniature laser ablation ionization mass spectrometer (LIMS), originally designed and developed for in situ space exploration. An ultrashort pulsed laser system (? ? 190 fs, ? = 775 nm) was used for ablation and ionization of sample material. We show that with our LIMS system, quantitative chemical mass spectrometric analysis with an ablation rate at the subnanometer level per single laser shot can be conducted. The measurement capabilities of our instrument, including the high vertical depth resolution coupled with high detection sensitivity of ?10 ppb, high dynamic range ?10(8), measurement accuracy and precision, is of considerable interest in various fields of application, where investigations with high lateral and vertical resolution of the chemical composition of solid materials are required, these include, e.g., wafers from semiconductor industry or studies on space weathered samples in space research. PMID:25642789

  13. Characterization of polymethoxylated flavones in Fructus aurantii by liquid chromatography with atmospheric pressure chemical ionization combined with tandem mass spectrometry

    Microsoft Academic Search

    Da-Yong Zhou; De-Liang Chen; Qing Xu; Xing-Ya Xue; Fei-Fang Zhang; Xin-Miao Liang

    2007-01-01

    Atmospheric pressure chemical ionization mass spectrometry (APCI-MS) was operated in positive mode (PI) to characterize polymethoxylated flavonoids (PMFs) through its specific radical cations by collision-induced dissociation (CID). The fragments of [M+H?n×15]+ produced by loss of one or more methyl group from the protonated molecule, as well as [M+H?29]+, [M+H?31]+, [M+H?33]+, [M+H?43]+, [M+H?46]+, and [M+H?61]+ fragment ions were detected, which were

  14. Validity of Saha's equation of thermal ionization for negatively charged spherical particles in complex plasmas in thermal equilibrium

    SciTech Connect

    Sodha, M. S.; Mishra, S. K. [DST Project, Department of Education Building, Lucknow University, Lucknow 226 007 (India)

    2011-04-15

    The authors have discussed the validity of Saha's equation for the charging of negatively charged spherical particles in a complex plasma in thermal equilibrium, even when the tunneling of the electrons, through the potential energy barrier surrounding the particle is considered. It is seen that the validity requires the probability of tunneling of an electron through the potential energy barrier surrounding the particle to be independent of the direction (inside to outside and vice versa) or in other words the Born's approximation should be valid.

  15. Negative thermal expansion in functional materials: controllable thermal expansion by chemical modifications.

    PubMed

    Chen, Jun; Hu, Lei; Deng, Jinxia; Xing, Xianran

    2015-05-26

    Negative thermal expansion (NTE) is an intriguing physical property of solids, which is a consequence of a complex interplay among the lattice, phonons, and electrons. Interestingly, a large number of NTE materials have been found in various types of functional materials. In the last two decades good progress has been achieved to discover new phenomena and mechanisms of NTE. In the present review article, NTE is reviewed in functional materials of ferroelectrics, magnetics, multiferroics, superconductors, temperature-induced electron configuration change and so on. Zero thermal expansion (ZTE) of functional materials is emphasized due to the importance for practical applications. The NTE functional materials present a general physical picture to reveal a strong coupling role between physical properties and NTE. There is a general nature of NTE for both ferroelectrics and magnetics, in which NTE is determined by either ferroelectric order or magnetic one. In NTE functional materials, a multi-way to control thermal expansion can be established through the coupling roles of ferroelectricity-NTE, magnetism-NTE, change of electron configuration-NTE, open-framework-NTE, and so on. Chemical modification has been proved to be an effective method to control thermal expansion. Finally, challenges and questions are discussed for the development of NTE materials. There remains a challenge to discover a "perfect" NTE material for each specific application for chemists. The future studies on NTE functional materials will definitely promote the development of NTE materials. PMID:25864730

  16. Experts workshop on the ecotoxicological risk assessment of ionizable organic chemicals: Towards a science-based framework for chemical assessment

    EPA Science Inventory

    There is a growing need to develop analytical methods and tools that can be applied to assess the environmental risks associated with charged, polar, and ionisable organic chemicals, such as those used as active pharmaceutical ingredients, biocides, and surface active chemicals. ...

  17. Room temperature chemical synthesis of highly oriented PbSe nanotubes based on negative free energy of formation

    Microsoft Academic Search

    B. R. Sankapal; R. D. Ladhe; D. B. Salunkhe; P. K. Baviskar; V. Gupta; S. Chand

    2011-01-01

    The sacrificial template free chemical synthesis of PbSe nanotubes at room temperature has been performed by lead hydroxination from cadmium hydroxide nanowires. This process was based on the ion exchange reaction to replace Cd2+ with Pb2+ ions from hydroxyl group followed by replacement of hydroxyl group with selenium ions. The reaction kinetics was accomplished due to more negative free energy

  18. Determination of nitrosamines in water by gas chromatography/chemical ionization/selective ion trapping mass spectrometry.

    PubMed

    Pozzi, Romina; Bocchini, Paola; Pinelli, Francesca; Galletti, Guido C

    2011-04-01

    A gas chromatography/mass spectrometry (GC/MS) method for determination of nine N-nitrosamines (NAs) in water is described. Two ionization modes, electron impact (EI) and chemical ionization (CI) with methanol, as well as different ion analysis techniques, i.e. full scan, selected ion storage (SIS) and tandem mass spectrometry (MS/MS) were tested. Chemical ionization followed by SIS resulted the mass spectrometric method of choice, with detection limits in the range of 1-2ng/L. Solid Phase Extraction (SPE) with coconut charcoal cartridges was applied to extract NAs from real samples, according EPA Method 521. Drinking water samples were collected from seven surface- and two groundwater treatment plants. Three surface water treatment plants were sampled before and after addition of O(3)/ClO(2) to observe the effect of disinfection on NAs' formation. N-nitrosodiethylamine (NDEA), n-nitrosodipropylamine (NDPA), n-nitrosomorpholine (NMOR) and n-nitrosodibutylamine (NDBA) were found up to concentrations exceeding three times the risk level of 10ng/L set by the California Department of Public Health. Because dermal adsorption has been recently indicated as a new contamination route of exposure to NAs for people who practice swimming activity, water samples from five swimming pools in the Bologna (Italy) area were collected. N-nitrosopyrrolidine (NPYR) was detected in all samples at concentrations larger than 50ng/L, likely as a disinfection by-product from the amino acid precursor proline, a main constituent of skin collagen. PMID:21377686

  19. Determination of 3-methyl-2,4-nonanedione in red wines using methanol chemical ionization ion trap mass spectrometry.

    PubMed

    Pons, Alexandre; Lavigne, Valérie; Darriet, Philippe; Dubourdieu, Denis

    2011-09-28

    A compound associated with oxidized flavor in red wines was recently-identified as 3-methyl-2,4-nonanedione (MND). In order to quantify it, positive chemical ionization (PCI) in an ion trap was studied using conventional liquid reagents such as methanol, acetonitrile, and acetone, as well as non-conventional liquid reagents such as ethyl acetate, diethyl ether, pentane, isohexane, and heptane. Under laboratory conditions, very different response factors were obtained with MND depending on the gas. We also compared the detection limit of conventional CI with hybrid chemical ionization (HCI). Finally, this compound was quantified in red wines by liquid/liquid extraction without any derivatization steps, followed by GC/MS-CI analysis, using methanol as the reagent gas. Coelutions of compounds with the same m/z were checked using methanol-d(4). The method we developed was linear in the 10-300 ng/L range of MND concentrations, with satisfactory repeatability. The detection limit was 4.3 ng/L, over 3 times lower than the olfactory perception threshold of this compound (16 ng/L). The suitability of this method for assaying this diketone in red wine was demonstrated by the analyzing many wines from different vintages. PMID:21871629

  20. A sensitive negative-ion electrospray ionization mass spectrometry detection for metallothionein in tris(hydroxymethyl)aminomethane acetate buffer

    NASA Astrophysics Data System (ADS)

    Shen, Jin-Can; Lu, Su-Ge; Zhuang, Zhi-Xia; Wang, Xiao-Ru; Lee, Frank S. C.

    2005-05-01

    Although positive-ion (PI) electrospray ionisation mass spectrometry (ESI-MS) has been usually applied for the analysis of native metallothioneins (MT) isoforms binding with metal ions, it suffers from the lack of insensitivity under neural conditions because of the low efficiency of protonation during ESI process. In this study, multiply deprotonated metallothionein (Zn7-MT-2a), produced from tris(hydroxymethyl)aminomethane (TRIS) acetate solutions under near neutral condition, was analyzed by negative-ion (NI) ESI-MS. Compared with the ammonium acetate buffer system which has been normally used for ESI-MS experiments, the use of TRIS acetate buffer results in the formation of more abundant ions and higher charge states of MT-2a, and consequently higher intensity is attained. The sensitivity enhancement of the system could be explained by the high gas-phase proton affinity, small molecular volume of the anion (acetate), and the high hydrogen consumption by TRIS in the buffer system, which would all favor the deprotonation of the analyte during NI-ESI process. Factors that may affect the NI-ESI responses, such as acid added in buffer, pH and concentration of TRIS acetate had been evaluated, and the result showed that using acetic acid, lower pH under the pH range evaluated, higher concentration of TRIS acetate all favored the MS detection of MT-2a. Our finding sheds light on a buffer system that may offer substantial sensitivity advantages in the studying of weakly bound, non-covalent complexes such as metal binding MTs, which are usually analyzed under near neutral conditions.

  1. In-source fragmentation of partially oxidized mono- and polycyclic aromatic hydrocarbons in atmospheric pressure chemical ionization mass spectrometry coupled to liquid chromatography

    PubMed

    Letzel; Poschl; Rosenberg; Grasserbauer; Niessner

    1999-01-01

    Partially oxidized derivatives of polycyclic aromatic hydrocarbons (PAHs) are known to be important environmental pollutants. For the identification of these substances in complex mixtures, e.g. atmospheric aerosol samples, liquid chromatography/mass spectrometry with atmospheric pressure chemical ionization (LC/APCI-MS) has been found to be a suitable analytical technique. In this study 31 derivatives of mono- and polycyclic aromatic hydrocarbons with up to five condensed aromatic rings carrying different functional groups (carboxyl, dicarboxylic anhydride, lactone, hydroxyl, and carbonyl) were characterized by LC/APCI-MS. Each substance was measured in positive and negative ion detection mode at four different fragmentor voltages (90 to 190 V). For the first time, the results show that characteristic and well-interpretable fragmentation patterns can be obtained for these classes of compounds by in-source collision-induced dissociation in a single quadrupole LC/APCI-MS system. For each class of compounds typical spectral features and optimum measurement conditions are reported, and fragmentation pathways are proposed. The study demonstrates the applicability of LC/APCI-MS for the determination of most of the investigated compounds at trace levels, and it provides a database for the identification of unknown partially oxidized aromatic hydrocarbons. Copyright 1999 John Wiley & Sons, Ltd. PMID:10589094

  2. Facilities: NHMFL 9.4 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer Citation: Characterization of Pine Pellet and Peanut Hull Pyrolysis of Bio-Oils by Negative-Ion Electrospray Ionization Fourier

    E-print Network

    Weston, Ken

    : Characterization of Pine Pellet and Peanut Hull Pyrolysis of Bio-Oils by Negative-Ion Electrospray Ionization pine pellets and peanut hulls, generates a hydrocarbon-rich liquid product (bio-oil) consisting of oily for thousands of compounds. Pine pellet bio-oils are dominated by species containing multiple oxygen atoms

  3. Comparison of quantum-mechanical and classical trajectory calculations of cross sections for ion-atom impact ionization of negative and positive ions for heavy-ion fusion applications

    E-print Network

    Kaganovich, Igor

    -atom impact ionization of negative and positive ions for heavy-ion fusion applications Igor D. KaganovichComparison of quantum-mechanical and classical trajectory calculations of cross sections for ion of quantum mechanics for the outer shell electrons of 3.2 GeV I and Cs ions. A large difference in cross

  4. High-resolution chemical ionization mass spectrometry (ToF-CIMS): application to study SOA composition and processing

    NASA Astrophysics Data System (ADS)

    Aljawhary, D.; Lee, A. K. Y.; Abbatt, J. P. D.

    2013-11-01

    This paper demonstrates the capabilities of chemical ionization mass spectrometry (CIMS) to study secondary organic aerosol (SOA) composition with a high-resolution (HR) time-of-flight mass analyzer (aerosol-ToF-CIMS). In particular, by studying aqueous oxidation of water-soluble organic compounds (WSOC) extracted from ?-pinene ozonolysis SOA, we assess the capabilities of three common CIMS reagent ions: (a) protonated water clusters (H2O)nH+, (b) acetate CH3C(O)O- and (c) iodide water clusters I(H2O)n- to monitor SOA composition. Furthermore, we report the relative sensitivity of these reagent ions to a wide range of common organic aerosol constituents. We find that (H2O)nH+ is more selective to the detection of less oxidized species, so that the range of O / C and OSC (carbon oxidation state) in the SOA spectra is considerably lower than those measured using CH3C(O)O- and I(H2O)n-. Specifically, (H2O)nH+ ionizes organic compounds with OSC ? 1.3, whereas CH3C(O)O- and I(H2O)n- both ionize highly oxygenated organics with OSC up to 4 with I(H2O)n- being more selective towards multi-functional organic compounds. In the bulk O / C and H / C space (in a Van Krevelen plot), there is a remarkable agreement in both absolute magnitude and oxidation trajectory between ToF-CIMS data and those from a high-resolution aerosol mass spectrometer (HR-AMS). Despite not using a sensitivity-weighted response for the ToF-CIMS data, the CIMS approach appears to capture much of the chemical change occurring. As demonstrated by the calibration experiments with standards, this is likely because there is not a large variability in sensitivities from one highly oxygenated species to another, particularly for the CH3C(O)O- and I(H2O)n- reagent ions. Finally, the data illustrate the capability of aerosol-ToF-CIMS to monitor specific chemical change, including the fragmentation and functionalization reactions that occur during organic oxidation, and the oxidative conversion of dimeric SOA species into monomers. Overall, aerosol-ToF-CIMS is a valuable, selective complement to some common SOA characterization methods, such as AMS and spectroscopic techniques. Both laboratory and ambient SOA samples can be analyzed using the techniques illustrated in the paper.

  5. Analysis of toxic norditerpenoid alkaloids in Delphinium species by electrospray, atmospheric pressure chemical ionization, and sequential tandem mass spectrometry.

    PubMed

    Gardner, D R; Panter, K E; Pfister, J A; Knight, A P

    1999-12-01

    A rapid electrospray mass spectrometry method was developed for screening larkspur (Delphinium spp.) plant material for toxic norditerpenoid alkaloids. The method was calibrated using two standard alkaloids, methyllycaconitine (1) and deltaline (2), with a recovery of 92% from spiked samples and relative standard deviations of 6.0% and 8.1% for the two alkaloids, respectively. Thirty-three samples of plains larkspur, Delphinium geyeri, were analyzed. Methyllycaconitine (1) concentration was 0.27% +/- 0.08% during a 1-month period in 1997 establishing the relative risk of poisoning from the plant to be low. The method was also applied to the trace analysis (<1 ppm) of 1 in serum samples from sheep dosed different levels of the alkaloid. Electrospray ionization combined with sequential tandem mass spectrometry and HPLC coupled to atmospheric pressure chemical ionization (APCI) mass spectrometry were used to detect and tentatively identify three new norditerpenoid alkaloids from Delphinium nuttallianum [bearline (6), 14-acetylbearline (7), 16-deacetylgeyerline (8)]. The tentative structure of the new alkaloids was predicted from the tandem mass spectra fragmentation patterns and assigning the substitution pattern for methoxy and acetyl groups at the C-14 and C-16 carbons. PMID:10606571

  6. Accurate quantitation of pentaerythritol tetranitrate and its degradation products using liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Brust, Hanneke; van Asten, Arian; Koeberg, Mattijs; Dalmolen, Jan; van der Heijden, Antoine; Schoenmakers, Peter

    2014-04-18

    After an explosion of pentaerythritol tetranitrate (PETN), its degradation products pentaerythritol trinitrate (PETriN), dinitrate (PEDiN) and mononitrate (PEMN) were detected using liquid chromatography-atmospheric-pressure chemical-ionization-mass spectrometry (LC-APCI-MS). Discrimination between post-explosion and naturally degraded PETN could be achieved based on the relative amounts of the degradation products. This information can be used as evidence when investigating a possible relationship between a suspect and a post-explosion crime scene. The present work focuses on accurate quantitation of PETN and its degradation products, using PETriN, PEDiN and PEMN standards specifically synthesized for this purpose. With the use of these standards, the ionization behavior of these compounds was studied, and a quantitative method was developed. Quantitation of PETN and trace levels of its degradation products was shown to be possible with accuracy between 85.7% and 103.7% and a precision ranging from 1.3% to 11.5%. The custom-made standards resulted in a more robust and reliable method to discriminate between post-explosion and naturally-degraded PETN. PMID:24656542

  7. Isotopologue analysis of sugar phosphates in yeast cell extracts by gas chromatography chemical ionization time-of-flight mass spectrometry.

    PubMed

    Chu, Dinh Binh; Troyer, Christina; Mairinger, Teresa; Ortmayr, Karin; Neubauer, Stefan; Koellensperger, Gunda; Hann, Stephan

    2015-04-01

    Metabolic flux analysis is based on the measurement of isotopologue ratios. In this work, a new GC-MS-based method was introduced enabling accurate determination of isotopologue distributions of sugar phosphates in cell extracts. A GC-TOFMS procedure was developed involving a two-step online derivatization (ethoximation followed by trimethylsilylation) offering high mass resolution, high mass accuracy and the potential of retrospective data analysis typical for TOFMS. The information loss due to fragmentation intrinsic for isotopologue analysis by electron ionization could be overcome by chemical ionization with methane. A thorough optimization regarding pressure of the reaction gas, emission current, electron energy and temperature of the ion source was carried out. For a substantial panel of sugar phosphates both of the glycolysis and the pentose phosphate pathway, sensitive determination of the protonated intact molecular ions together with low abundance fragment ions was successfully achieved. The developed method was evaluated for analysis of Pichia pastoris cell extracts. The measured isotopologue ratios were in the range of 55:1-2:1. The comparison of the experimental isotopologue fractions with the theoretical fractions was excellent, revealing a maximum bias of 4.6% and an average bias of 1.4%. PMID:25673246

  8. REDUCTION OF TOXIC AND UNDESIRABLE CHEMICAL COMPOUNDS IN FOOD BY IONIZING IRRADIATION

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Possible toxic and carcinogenic chemicals such as furan, acrylamide, nitrosamines, biogenic amines, and mycotoxins (aflatoxin B1, patulin, fumonisin, etc.) can accumulate in various foods during thermal processing, preservation and storage. Recent studies have suggested that irradiation reduces leve...

  9. Detection of amphetamines in urine using head space-solid phase microextraction and chemical ionization selected ion monitoring.

    PubMed

    Yashiki, M; Kojima, T; Miyazaki, T; Nagasawa, N; Iwasaki, Y; Hara, K

    1995-12-29

    An accurate, simple and rapid method for qualitative and quantitative analysis of amphetamine and methamphetamine in urine was developed using head space-solid phase microextraction and gas chromatography-mass spectrometry/chemical ionization selected iron monitoring. A vial containing a urine sample potassium carbonate and pentadeuterated methamphetamine which was used as an internal standard was heated at 80 degrees C for 20 min. The needle of a solid phase microextraction device was passed through the septum, and the extraction fiber in the needle was exposed for 5 min in the head space of the vial. The needle was removed from the vial and inserted into the injection port of gas chromatograph or gas chromatograph/mass spectrometer. The compounds adsorbed on the fiber were detached by exposing the fiber in the injection port, and analyzed. The proposed method was more than 20 times more sensitive than the conventional head space method. PMID:8566919

  10. Primary Ion Depletion Kinetics (PIDK) Studies as a New Tool for Investigating Chemical Ionization Fragmentation Reactions with PTR-MS

    PubMed Central

    Schuhfried, Erna; Märk, Tilmann D.; Biasioli, Franco

    2013-01-01

    We report on a new approach for studying fragmentation channels in Proton Transfer Reaction-Mass Spectrometry (PTR-MS), which we name primary ion depletion kinetics (PIDK). PTR-MS is a chemical ionization mass spectrometric (CIMS) technique deploying hydronium ions for the chemical ionization. Induced by extremely high concentrations of analyte M, depletion of the primary ions in the drift tube occurs. This is observed as quasi zero concentration of the primary ion H3O+, and constant MH+. Under these non-standard conditions, we find an overall changed fragmentation. We offer two explanations. Either the changed fragmentation pattern is the result of secondary proton transfer reactions. Or, alternatively, the fast depletion of H3O+ leads to reduced heating of H3O+ in the drift field, and consequently changed fragmentation following protonation of the analyte M. In any case, we use the observed changes in fragmentation as a successful new approach to fragmentation studies, and term it primary ion depletion kinetics, PIDK. PIDK easily yields an abundance of continuous data points with little deviation, because they are obtained in one experimental run, even for low abundant fragments. This is an advantage over traditional internal kinetic energy variation studies (electric field per number density (E/N) variation studies). Also, some interpretation on the underlying fragmentation reaction mechanisms can be gleamed. We measure low occurring fragmentation (<2% of MH+) of the compounds dimethyl sulfide, DMS, a compound that reportedly does not fragment, diethyl sulfide DES, and dipropyl sulfide DPS. And we confirm and complement the results with traditional E/N studies. Summing up, the new approach of primary ion depletion kinetics allows for the identification of dehydrogenation [MH+ -H2] and adduct formation (RMH+) as low abundant fragmentation channels in monosulfides. PMID:23840555

  11. Rapid screening method for intact glucosinolates in Chinese medicinal herbs by using liquid chromatography coupled with electrospray ionization ion trap mass spectrometry in negative ion mode.

    PubMed

    Lee, Kim-Chung; Chan, Wan; Liang, Zhitao; Liu, Ning; Zhao, Zhongzhen; Lee, Albert Wai-Ming; Cai, Zongwei

    2008-09-01

    An optimized method using liquid chromatography coupled with electrospray ionization ion trap mass spectrometry (LC/ESI-ITMS) in negative ion mode has been developed for screening different structural classes of intact glucosinolates in six Chinese medicinal herbs. The glucosinolates were extracted with hot methanol/water (70:30 v/v) and separation of the individual glucosinolates was achieved using a reversed-phase C18 column with an aqueous ammonium acetate/methanol gradient. Identification of the intact glucosinolates was based on the detection of compounds with a constant neutral loss of 242 Da corresponding to the combined loss of anhydroglucose (162 Da) and sulfur trioxide (80 Da) in collision-induced dissociation. The structures of the identified glucosinolates were confirmed with the use of group-specific product ions at m/z 195, 241, 259, 275 in their corresponding MS/MS product ion spectra. Differentiation of intact glucosinolates was achieved through their respective retention times and molecular masses as well as the characteristic product ions. The limits of detection were at the low nanogram level per injection, based on constant neutral loss scans. Significant variation in the compositions of intact glucosinolates was identified in the cruciferous herbs. This method was applied in the differentiation and quality control of two pairs of easily confused herbs. PMID:18711760

  12. Potential of atmospheric pressure chemical ionization source in GC-QTOF MS for pesticide residue analysis.

    PubMed

    Portolés, T; Sancho, J V; Hernández, F; Newton, A; Hancock, P

    2010-08-01

    The potential applications of a new atmospheric pressure source for GC-MS analysis have been investigated in this work. A list of around 100 GC-amenable pesticides, which includes organochlorine, organophosphorus and organonitrogenated compounds, has been used to evaluate their behavior in the new source. Favoring the major formation of the molecular ion in the source has been the main goal due to the wide-scope screening possibilities that this fact brings in comparison with the traditional, highly fragmented electron ionization spectra. Thus, the addition of water as modifier has been tested as a way to promote the generation of protonated molecules. Pesticides investigated have been classified into six groups according to their ionization/fragmentation behavior. Four of them are characterized by the abundant formation of the protonated molecule in the atmospheric pressure source, mostly being the base peak of the spectrum. These results show that wide-scope screening could be easily performed with this source by investigating the presence of the protonated molecule ion, MH+. The developed procedure has been applied to pesticide screening in different food samples (nectarine, orange and spinach) and it has allowed the presence of several pesticides to be confirmed such as chlorpyriphos ethyl, deltamethrin and endosulfan sulfate. The availability of a quadrupole time-of-flight instrument made it feasible to perform additional MS/MS experiments for both standards and samples to go further in the confirmation of the identity of the detected compounds. Results shown in this paper have been obtained using a prototype source which exhibits promising features that could be applied to other analytical problems apart from those illustrated in this work. PMID:20641006

  13. Analysis of intact tetraether lipids in archaeal cell material and sediments by high performance liquid chromatography\\/atmospheric pressure chemical ionization mass spectrometry

    Microsoft Academic Search

    J. S. Sinninghe Damsté; E. C. Hopmans; S. Schouten; R. D. Pancost; M. T. J. van der Meer

    2000-01-01

    A method combining normal phase high performance liquid chromatography (HPLC) with positive ion atmospheric pressure chemical ionization mass spectrometry (APCI-MS) was developed for the analysis of intact glycerol dialkyl glycerol tetraethers (GDGTs) in archaeal cell material and sediments. All GDGTs previously reported to occur in the thermophilic archaeon Sulfolobus solfataricus could be identified based on their mass spectra and retention

  14. Experts Workshop on the Ecotoxicological Risk Assessment of Ionizable Organic Chemicals: Bioaccumulation/ADME

    EPA Science Inventory

    The bioaccumulation potential of neutral organic chemicals (e.g., PCBs, DDT, brominated flame retardants) has received a great deal of attention from scientists in the field of environment toxicology and chemistry over the past four decades. Regulations based on our understanding...

  15. Evaluation of sensitivity for positive tone non-chemically and chemically amplified resists using ionized radiation: EUV, x-ray, electron and ion induced reactions

    NASA Astrophysics Data System (ADS)

    Oshima, Akihiro; Oyama, Tomoko Gowa; Washio, Masakazu; Tagawa, Seiichi

    2013-03-01

    The different exposure sources induce a different energy deposition in resist materials. Linear energy transfer (LET) effect for resist sensitivity is very important issue from the viewpoint of radiation induced chemical reactions for high-volume nanofabrication. The sensitivities of positive tone non-chemically (non-CA, ZEP) and chemically amplified (CA, UV-3) resist materials are evaluated using various ionized radiation such as EUV, soft X-rays, EB and various ion beams. Since the notations of sensitivity of resist vary with exposure sources, in order to evaluate systematically, the resist sensitivity were estimated in terms of absorbed dose in resist materials. Highly-monochromated EUV and soft X-rays (6.7 nm - 3.1 nm) from the BL27SU of the SPring-8, high energy ion beams (C6+, Ne10+, Mg12+, Si14+ , Ar18+, Kr36+ and Xe54+) with 6 MeV/u from MEXP of HIMAC, EB from low energy EB accelerator (Hamamatsu Photonics, EB-engine®, 100 kV) and EB lithography system (30 keV and 75keV) were used for the exposure. For non-CA and CA resist materials, it was found that LET effects for sensitivity would be hardly observed except for heavier ion beams. Especially, in the case of the high energy ion beam less than Si14+ with 6 MeV/u, it is suggested that the radiation induced chemical reaction would be equivalent to EUV, soft X-ray and EB exposure. Hence, it indicates that the resist sensitivity could be systematically evaluated by absorbed dose in resist materials.

  16. Novel electrolysis-ionized-water cleaning technique for the chemical-mechanical polishing (CMP) process

    Microsoft Academic Search

    H. Aoki; T. Nakajima; K. Kikuta; Y. Hayashi

    1994-01-01

    Recently, chemical-mechanical-polishing (CMP) technology has become more and more important as device packing-density has increased. This is because the CMP of interlayer dielectrics realizes global planarization resulting in multi-level interconnections with finer pitches. However, effective wafer surface cleaning for particles and contamination is needed because slurries with colloidal silica particles are used during the CMP processing. Though wafer cleaning by

  17. The first UK measurements of nitryl chloride using a chemical ionization mass spectrometer in central London in the summer of 2012, and an investigation of the role of Cl atom oxidation

    NASA Astrophysics Data System (ADS)

    Bannan, Thomas J.; Booth, A. Murray; Bacak, Asan; Muller, Jennifer B. A.; Leather, Kimberley E.; Le Breton, Michael; Jones, Benjamin; Young, Dominique; Coe, Hugh; Allan, James; Visser, Suzanne; Slowik, Jay G.; Furger, Markus; Prévôt, André S. H.; Lee, James; Dunmore, Rachel E.; Hopkins, James R.; Hamilton, Jacqueline F.; Lewis, Alastair C.; Whalley, Lisa K.; Sharp, Thomas; Stone, Daniel; Heard, Dwayne E.; Fleming, Zoë L.; Leigh, Roland; Shallcross, Dudley E.; Percival, Carl J.

    2015-06-01

    The first nitryl chloride (ClNO2) measurements in the UK were made during the summer 2012 ClearfLo campaign with a chemical ionization mass spectrometer, utilizing an I- ionization scheme. Concentrations of ClNO2 exceeded detectable limits (11 ppt) every night with a maximum concentration of 724 ppt. A diurnal profile of ClNO2 peaking between 4 and 5 A.M., decreasing directly after sunrise, was observed. Concentrations of ClNO2 above the detection limit are generally observed between 8 P.M. and 11 A.M. Different ratios of the production of ClNO2:N2O5 were observed throughout with both positive and negative correlations between the two species being reported. The photolysis of ClNO2 and a box model utilizing the Master Chemical Mechanism modified to include chlorine chemistry was used to calculate Cl atom concentrations. Simultaneous measurements of hydroxyl radicals (OH) using low pressure laser-induced fluorescence and ozone enabled the relative importance of the oxidation of three groups of measured VOCs (alkanes, alkenes, and alkynes) by OH radicals, Cl atoms, and O3 to be compared. For the day with the maximum calculated Cl atom concentration, Cl atoms in the early morning were the dominant oxidant for alkanes and, over the entire day, contributed 15%, 3%, and 26% toward the oxidation of alkanes, alkenes, and alkynes, respectively.

  18. Negative thermal ion mass spectrometry of osmium, rhenium, and iridium

    NASA Technical Reports Server (NTRS)

    Creaser, R. A.; Papanastassiou, D. A.; Wasserburg, G. J.

    1991-01-01

    This paper describes a technique for obtaining, in a conventional surface ionization mass spectrometer, intense ion beams of negatively charged oxides of Os, Re, and Ir by thermal ionization. It is shown that the principal ion species of these ions are OsO3(-), ReO4(-), and IrO2(-), respectively. For Re-187/Os-187 studies, this technique offers the advantage of isotopic analyses without prior chemical separation of Re from Os.

  19. Screening for forensically relevant benzodiazepines in human hair by gas chromatography-negative ion chemical ionization-mass spectrometry

    Microsoft Academic Search

    V. Cirimele; P. Kintz; B. Ludes

    1997-01-01

    A procedure is presented for the detection in human hair of forensically relevant benzodiazepines, i.e. nordiazepam, oxazepem, bromazepam, diazepam, lorazepam, flunitrazepam, alprazolam and triazolam. The method involves decontamination of hair with methylene chloride, pulverization in a ball mill, incubation of 50 mg powdered hair in Soerensen buffer (pH 7.6) in the presence of prazepam-d5 used as internal standard, liquid-liquid extraction

  20. Influence of negative Poisson's ratio (Auxetics) on cell behavior Pranav Soman, Biomedical and Chemical Engineering

    E-print Network

    Mather, Patrick T.

    , and 3D printing technologies. Firstly, Dynamic Projection printing or Nozzle-based extrusion printing goal of having these replace pathological tissues. Materials property of an ideal scaffold must is assumed to be positive for all materials (~0.3 to 0.5), even though materials with negative Poisson

  1. Development of a gas-cylinder-free plasma desorption/ionization system for on-site detection of chemical warfare agents.

    PubMed

    Iwai, Takahiro; Kakegawa, Ken; Aida, Mari; Nagashima, Hisayuki; Nagoya, Tomoki; Kanamori-Kataoka, Mieko; Miyahara, Hidekazu; Seto, Yasuo; Okino, Akitoshi

    2015-06-01

    A gas-cylinder-free plasma desorption/ionization system was developed to realize a mobile on-site analytical device for detection of chemical warfare agents (CWAs). In this system, the plasma source was directly connected to the inlet of a mass spectrometer. The plasma can be generated with ambient air, which is drawn into the discharge region by negative pressure in the mass spectrometer. High-power density pulsed plasma of 100 kW could be generated by using a microhollow cathode and a laboratory-built high-intensity pulsed power supply (pulse width: 10-20 ?s; repetition frequency: 50 Hz). CWAs were desorbed and protonated in the enclosed space adjacent to the plasma source. Protonated sample molecules were introduced to the mass spectrometer by airflow through the discharge region. To evaluate the analytical performance of this device, helium and air plasma were directly irradiated to CWAs in the gas-cylinder-free plasma desorption/ionization system and the protonated molecules were analyzed by using an ion-trap mass spectrometer. A blister agent (nitrogen mustard 3) and nerve gases [cyclohexylsarin (GF), tabun (GA), and O-ethyl S-2-N,N-diisopropylaminoethyl methylphosphonothiolate (VX)] in solution in n-hexane were applied to the Teflon rod and used as test samples, after solvent evaporation. As a result, protonated molecules of CWAs were successfully observed as the characteristic ion peaks at m/z 204, 181, 163, and 268, respectively. In air plasma, the limits of detection were estimated to be 22, 20, 4.8, and 1.0 pmol, respectively, which were lower than those obtained with helium plasma. To achieve quantitative analysis, calibration curves were made by using CWA stimulant dipinacolyl methylphosphonate as an internal standard; straight correlation lines (R(2) = 0.9998) of the peak intensity ratios (target per internal standard) were obtained. Remarkably, GA and GF gave protonated dimer ions, and the ratios of the protonated dimer ions to the protonated monomers increased with the amount of GA and GF applied. PMID:25958918

  2. Determination of total nitrofuran metabolites in shrimp muscle using liquid chromatography/tandem mass spectrometry in the atmospheric pressure chemical ionization mode.

    PubMed

    An, Haejung; Henry, Mark; Cain, Teresa; Tran, Bichsa; Paek, Han Chol; Farley, Dennis

    2012-01-01

    The method of MacMahon and Lohne for analysis of nitrofuran metabolites in shrimp was optimized to streamline the extraction processes and the LC analysis. This revised method includes 16 h of mild acid hydrolysis/derivatization followed by ethyl acetate extraction and analysis by LC/MS/MS in the atmospheric pressure chemical ionization mode. This revised method was validated in shrimp for concentrations of 0.25 to 2.0 ng/g. The LOQ was 0.25 ng/g for all metabolites. The LOD was 0.052 nglg for 1-aminohydantoin (AHD), 0.206 ng/g for 3-amino-2-oxazolidinone (AOZ), 0.108 ng/g for semicarbazide (SC), and 0.062 ng/g for 3-amino-5-morpholinomethyl-2-oxazolidinone (AMOZ). The spike recoveries with RSD into negative matrix at 1 ng/g were 100.2% (3.2%) for AHD, 102.5% (1.0%) for AOZ, 103.7% (2.3%) for SC, and 104.0% (3.3%) for AMOZ. The spike recoveries at 1 ng/g into unknown samples (n=108) containing varied levels of nitrofuran metabolites were 112.6% (25.7%) for AHD, 108.1% (12.1%) for AOZ, 103.0% (12.0%) for SC, and 100.3% (6.9%) for AMOZ. Interday precision with samples containing incurred AOZ concentrations of 0.92 to 17.8 ppb performed over a year was 10.4% RSD. The method is accurate and precise for determining nitrofuran concentrations in the edible tissue of shrimp. PMID:22970594

  3. Differentiation of Positional Isomers of Hybrid Peptides Containing Repeats of beta-Nucleoside Derived Amino Acid (beta-Nda-) and L-Amino Acids by Positive and Negative Ion Electrospray Ionization Tandem Mass Spectrometry (ESI-MS n )

    Microsoft Academic Search

    B. Raju; M. Ramesh; R. Srinivas; S. Chandrasekhar; N. Kiranmai; V. U. M. Sarma

    2011-01-01

    A new class of positional isomeric pairs of -Boc protected oligopeptides comprised of alternating nucleoside derived beta-amino acid (beta-Nda-) and L-amino acid residues (alanine, valine, and phenylalanine) have been differentiated by both positive and negative ion electrospray ionization ion-trap tandem mass spectrometry (ESI-MS n ). The protonated dipeptide positional isomers with beta-Nda- at the N-terminus lose CH3OH, NH3, and C2H4O2,

  4. Chemically amplified negative-tone photoresist for sub-half-micron device and mask fabrication

    Microsoft Academic Search

    Willard E. Conley; Robert Dundatscheck; Jeffrey D. Gelorme; John Horvat; Ronald M. Martino; Elizabeth Murphy; Anne Petrosky; Gary T. Spinillo; Kevin J. Stewart; Robert Wilbarg; Robert L. Wood

    1991-01-01

    In this paper we discuss a new alkaline soluble negative acting photoresist which incorporates a phenolic based resin, urea\\/formaldehyde prepolymer as a crosslinking agent and an organic acid-generating sensitizer. This system, dubbed 'EBX' (Electron Beam\\/X-ray) resist has demonstrated excellent lithographic properties in various exposure modes. Discussion will center on imaging characteristics in the deep and mid ultraviolet using Micrascan I

  5. Measurement of atmospheric amines and ammonia using the high resolution time-of-flight chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Zheng, Jun; Ma, Yan; Chen, Mindong; Zhang, Qi; Wang, Lin; Khalizov, Alexei F.; Yao, Lei; Wang, Zhen; Wang, Xing; Chen, Linxi

    2015-02-01

    Ammonia (NH3) and amines play important roles in the nucleation and growth of atmospheric aerosols. To identify the sources of these chemicals in the densely populated and industrialized Yangtze River Delta region of China, we conducted measurements of NH3 and several amines, including methylamine (CH3NH2), C2-amines (C2H7N), and C3-amines (C3H9N) at a suburban site of Nanjing, China, during summer 2012. Using a high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS, Aerodyne), 1-min-averaged concentrations of NH3 and amines ranged from a few parts per trillions by volume (pptv) to dozens of parts per billion by volume (ppbv). The average ± 1? concentrations of NH3 and total amines during the measurement period were 1.7 ± 2.3 ppbv and 7.2 ± 7.4 pptv, respectively. Among the amines, C2-amines were the most abundant, accounting for 54% of the total amine loading. Significant correlations between NH3 and all three types of amines (0.65 < r2 < 0.80) indicate similar emission sources. Analysis of meteorological conditions indicated that these NH3 and amine laden air masses mainly originated from nearby industrial areas where NH3 was used for selective catalytic reduction of nitrogen oxides (NOx). The results of this work indicate that industrial emissions in Nanjing, China may have a significant impact on local and regional aerosol chemistry by supplying considerable amount of amines.

  6. Determination of chlorantraniliprole residues in crops by liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry/mass spectrometry.

    PubMed

    Grant, Joann; Rodgers, Carol A; Chickering, Clark D; Hill, Sidney J; Stry, James J

    2010-01-01

    An analytical method is presented for the determination of chlorantraniliprole residues in crops. Chlorantraniliprole residues were extracted from crop matrixes with acetonitrile after a water soak. The extracts were passed through a strong anion-exchange (SAX) SPE cartridge stacked on top of a reversed-phase (RP) polymer cartridge. After both cartridges were rinsed and vacuum-dried, the SAX cartridge was removed, and chlorantraniliprole was eluted from the RP polymer cartridge with acetonitrile. The acetonitrile eluate was evaporated to dryness, reconstituted, and analyzed using an LC/MS/MS instrument equipped with an atmospheric pressure chemical ionization source. The method was successfully validated at 0.010, 0.10, and 10 mg/kg for the following crop matrixes: potatoes, sugar beets (tops), lettuce, broccoli, soybeans, soybean forage, tomatoes, cucumbers, oranges, apples, pears, peaches, almonds (nutmeat), rice grain, wheat grain, wheat hay, corn stover, alfalfa forage, cottonseed, grapes, and corn grain. The average recoveries from all crop samples fortified at the method LOQ ranged from 91 to 108%, with an overall average recovery of 97%. The average recoveries from all crop samples fortified at 10 times the method LOQ ranged from 89 to 115%, with an overall average recovery of 101%. For all of the fortified control samples analyzed in this study, the overall average recovery was 99%. PMID:20922964

  7. Self-Aspirated Atmospheric Pressure Chemical Ionization Source for Direct Sampling of Analytes on Surfaces and in Liquid Solutions

    SciTech Connect

    Asano, Keiji G [ORNL; Ford, Michael J [ORNL; Tomkins, Bruce A [ORNL; Van Berkel, Gary J [ORNL

    2005-01-01

    A self-aspirating heated nebulizer probe is described and demonstrated for use in the direct analysis of analytes on surfaces and in liquid samples by atmospheric pressure chemical ionization (APCI) mass spectrometry. Functionality and performance of the probe as a self-aspirating APCI source is demonstrated using reserpine and progesterone as test compounds. The utility of the probe to sample analytes directly from surfaces was demonstrated first by scanning development lanes of a reversed-phase thin-layer chromatography plate in which a three-component dye mixture, viz., Fat Red 7B, Solvent Green 3, and Solvent Blue 35, was spotted and the components were separated. Development lanes were scanned by the sampling probe operated under computer control (x, y plane) while full-scan mass spectra were recorded using a quadrupole ion trap mass spectrometer. In addition, the ability to sample the surface of pharmaceutical tablets (viz., Extra Strength Tylenol(reg. sign) and Evista(reg. sign) tablets) and to detect the active ingredients (acetaminophen and raloxifene, respectively) selectively was demonstrated using tandem mass spectrometry (MS/MS). Finally, the capability to sample analyte solutions from the wells of a 384-well microtiter plate and to perform quantitative analyses using MS/MS detection was illustrated with cotinine standards spiked with cotinine-d{sub 3} as an internal standard.

  8. Analysis of underivatized amphetamines and related phenethylamines with high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Bogusz, M J; Krüger, K D; Maier, R D

    2000-03-01

    Amphetamine, methamphetamine, illicit designer phenethylamines (MDA, MDEA, MDMA, MBDB, and BDMPEA), and other phenethylamines (benzyl-1-phenylethylamine, cathinone, ephedrine, fenfluramine, norfenfluramine, phentermine, 1-phenylethylamine, phenylpropanolamine, and propylhexedrine) were extracted from serum using a solid-phase extraction procedure. The extracts were examined with high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS). The drugs were separated on ODS column in acetonitrile/50 mM ammonium formate buffer (pH 3.0) (25:75) as a mobile phase. Full-scan mass spectra of drugs examined by means of APCI with collision-induced dissociation showed protonated molecular ions and fragments typical for particular drugs. LC-APCI-MS allowed an unequivocal differentiation of all drugs involved. The quantitation was performed using selected ion monitoring of protonated molecular ions and fragments of drugs involved and their deuterated analogues. The limits of detection ranged from 1 to 5 microg/L serum, and the recoveries ranged from 58 to 96%. A linear response was observed for all drugs in the range from 5 to 500 microg/L. The method was applied for routine determination of amphetamine, MDMA, MDA, and MDEA in one run. Solid-phase extraction used assured simultaneous isolation of various groups of basic drugs of forensic interest (opiates, cocaines, phenethylamines, and benzodiazepines) from biofluids. PMID:10732943

  9. Influence of ionizing radiation on physical properties of native and chemically modified starches

    NASA Astrophysics Data System (ADS)

    Henry, F.; Costa, L. C.; Aymes-Chodur, C.

    2010-01-01

    Cationic and anionic starches (chemically modified) and native starch (non-modified) were exposed to electron-beam irradiation at doses of 25, 75 and 150 kGy. The increasing solubility in water, due to chain scission and creation of polar groups as already mentioned in the literature, has been confirmed using several physical methodologies. Impedance Spectroscopy (IS) on water solutions was carried out in order to calculate the relaxation parameters of the Cole-Cole model and ? and ? parameters of the Jones-Dole equation, which show the influence of radiation dose on increasing polarity, decreasing of molecular mass and increasing of electrostatic attraction between chains. Infra-red spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC) confirm the formation of polar groups that retain water. The aim of this work was to confirm that the control of chain scission and functionalization of starches with irradiation could then be used in a future work to create nanoparticles by complex coacervation in an aqueous base.

  10. Neurochemical analysis of amino acids, polyamines and carboxylic acids: GC–MS quantitation of tBDMS derivatives using ammonia positive chemical ionization

    Microsoft Academic Search

    Paul L. Wood; M. Amin Khan; Joseph R. Moskal

    2006-01-01

    The GC–MS quantitation of a large number of neurochemicals utilizing a single derivatization step is not common but is provided by the reagent N-(tert-butyldimethylsilyl)-N-methyltrifluro-acetamide (MTBSTFA). Previous workers have utilized this derivative for GC–MS analyses of amino acids, carboxylic acids and urea with electron impact (EI) and with positive chemical ionization (PCI; methane as reagent gas). However, these conditions yield significant

  11. Sensitive and specific determination of clindamycin in human serum and bone tissue applying liquid chromatography–atmospheric pressure chemical ionization–mass spectrometry

    Microsoft Academic Search

    J. Martens-Lobenhoffer; P. Banditt

    2001-01-01

    A method for the quantification of clindamycin in human serum and in human bone tissue samples applying high-performance liquid chromatography with atmospheric pressure chemical ionization–mass spectrometry (APCI–MS) is presented. Lincomycin is used as the internal standard. Serum samples are prepared only by protein precipitation with acetonitrile. Bone tissue samples have to be crushed and homogenized in extraction buffer prior to

  12. Quantitative analysis of levamisole in porcine tissues by high-performance liquid chromatography combined with atmospheric pressure chemical ionization mass spectrometry

    Microsoft Academic Search

    Marc Cherlet; Siegrid De Baere; Siska Croubels; Patrick De Backer

    2000-01-01

    This work presents the development and the validation of an LC–MS–MS method with atmospheric pressure chemical ionization for the quantitative determination of levamisole, an anthelmintic for veterinary use, in porcine tissue samples. A liquid–liquid back extraction procedure using hexane–isoamylalcohol (95:5, v\\/v) as extraction solvent was followed by a solid-phase extraction procedure using an SCX column to clean up the tissue

  13. Determination of imidacloprid, metalaxyl, myclobutanil, propham, and thiabendazole in fruits and vegetables by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry

    Microsoft Academic Search

    Ximo Pous; Yolanda Picó

    2001-01-01

    Imidacloprid, metalaxyl, myclobutanil, propham, and thiabendazole have been simultaneously determined in strawberries, oranges, potatoes, pears, and melons by matrix solid-phase dispersion (MSPD) followed by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) in positive-ion mode. The samples were homogenized with C8 bonded silica as MSPD sorbent, placed in a glass column, and eluted with dichloromethane. Chromatographic separation of the compounds was

  14. Multiple-stage mass spectrometric analysis of six pesticides in oranges by liquid chromatography–atmospheric pressure chemical ionization–ion trap mass spectrometry

    Microsoft Academic Search

    Cristina Blasco; Yolanda Picó

    2004-01-01

    Six pesticides were determined by liquid chromatography (LC) with positive ion (PI) atmospheric pressure chemical ionization quadrupole ion-trap tandem mass spectrometry (APCI–MS–MS). Ion fragmentation was studied by MS, MS2 and MS3. Fragmentation of the pesticides produced ions formed by various losses from the side-chains and through heterocyclic ring opening, but without any common fragmentation pathway. Multiple reaction monitoring (MRM) of

  15. Improved quantitative detection of 11 urinary phthalate metabolites in humans using liquid chromatography–atmospheric pressure chemical ionization tandem mass spectrometry

    Microsoft Academic Search

    Manori J Silva; Nicole A Malek; Carolyn C Hodge; John A Reidy; Kayoko Kato; Dana B Barr; Larry L Needham; John W Brock

    2003-01-01

    Phthalates are widely used as industrial solvents and plasticizers, with global use exceeding four million tons per year. We improved our previously developed high-performance liquid chromatography–atmospheric pressure chemical ionization-tandem mass spectrometric (HPLC–APCI-MS\\/MS) method to measure urinary phthalate metabolites by increasing the selectivity and the sensitivity by better resolving them from the solvent front, adding three more phthalate metabolites, monomethyl phthalate

  16. Determination of Melamine and Derivatives in Foods by Liquid Chromatography Coupled to Atmospheric Pressure Chemical Ionization Mass Spectrometry and Diode Array Detection

    Microsoft Academic Search

    Pilar Viñas; Natalia Campillo; Gema Férez-Melgarejo; Manuel Hernández-Córdoba

    2012-01-01

    Two liquid chromatographic methods based on atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) and diode array detection (DAD) are evaluated for the rapid determination of melamine (MEL) and structurally related compounds, including ammeline (AMN), ammelide (AMD) and cyanuric acid (CA) in foods. Both procedures used ion-exchange LC and isocratic elution. Samples were extracted by homogenization with acetonitrile\\/water\\/diethylamine. Specificity was demonstrated

  17. A Strategy to Locate Cysteine Residues in Proteins by Specific Chemical Cleavage Followed by Matrix-Assisted Laser Desorption\\/Ionization Time-of-Flight Mass Spectrometry

    Microsoft Academic Search

    Jiang Wu; Douglas A. Gage; J. Throck Watson

    1996-01-01

    A simple methodology has been developed to characterize the number and location of free cysteine and cystine groups in peptides and proteins, using chemical modification and matrix-assisted laser desorption\\/ionization time-of flight mass spectrometry (MALDI-TOF MS). This new approach employs a specific reaction between free sulfhydryls and 2-nitro-5-thiocyanobenzoic acid (NTCB) to selectively cyanylate cysteine thiols. The N-terminal peptide bond of the

  18. Quantitative analysis of adenosine using liquid chromatography\\/atmospheric pressure chemical ionization-tandem mass spectrometry (LC\\/APCI-MS\\/MS)

    Microsoft Academic Search

    Annelies Van Dycke; Alain Verstraete; Kristof Pil; Robrecht Raedt; Kristl Vonck; Detlev Boison; Paul Boon

    2010-01-01

    Adenosine-secreting cellular brain implants constitute a promising therapeutic approach for the treatment of epilepsy. To engineer neural stem cells for therapeutic adenosine delivery, a reliable and fast analytical method is necessary to quantify cell-based adenosine release. Here we describe the development, optimization and validation of adenosine measurement using liquid chromatography–atmospheric pressure chemical ionization-tandem mass spectrometry (LC–APCI-MS\\/MS). LC–MS\\/MS in positive ion

  19. Rapid and sensitive analysis of azadirachtin and related triterpenoids from Neem ( Azadirachta indica) by high-performance liquid chromatography–atmospheric pressure chemical ionization mass spectrometry

    Microsoft Academic Search

    Otmar Schaaf; Andrew P Jarvis; S. Andrew van der Esch; Germina Giagnacovo; Neil J Oldham

    2000-01-01

    Based on reversed-phase high-performance liquid chromatography (RP-HPLC) and atmospheric pressure chemical ionization (APCI) mass spectrometry, a HPLC–MS method was developed to permit the rapid qualitative and quantitative analysis of azadirachtin and related tetranortriterpenoids from seeds and tissue cultures of Neem (Azadirachta indica). APCI+ standard scanning mass spectra of the major Neem triterpenoids were recorded and utilized to select suitable ions

  20. Total microcystins analysis in water using laser diode thermal desorption-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Roy-Lachapelle, Audrey; Fayad, Paul B; Sinotte, Marc; Deblois, Christian; Sauvé, Sébastien

    2014-04-11

    A new approach for the analysis of the cyanobacterial microcystins (MCs) in environmental water matrices has been developed. It offers a cost efficient alternative method for the fast quantification of total MCs using mass spectrometry. This approach permits the quantification of total MCs concentrations without requiring any derivatization or the use of a suite of MCs standards. The oxidation product 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) was formed through a Lemieux oxidation and represented the total concentration of free and bound MCs in water samples. MMPB was analyzed using laser diode thermal desorption-atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). LDTD is a robust and reliable sample introduction method with ultra-fast analysis time (<15 s sample(-1)). Several oxidation and LDTD parameters were optimized to improve recoveries and signal intensity. MCs oxidation recovery yield was 103%, showing a complete reaction. Internal calibration with standard addition was achieved with the use of 4-phenylbutyric acid (4-PB) as internal standard and showed good linearity (R(2)>0.999). Limits of detection and quantification were 0.2 and 0.9 ?g L(-1), respectively. These values are comparable with the WHO (World Health Organization) guideline of 1 ?g L(-1) for total microcystin-LR congener in drinking water. Accuracy and interday/intraday variation coefficients were below 15%. Matrix effect was determined with a recovery of 91%, showing no significant signal suppression. This work demonstrates the use of the LDTD-APCI-MS/MS interface for the screening, detection and quantification of total MCs in complex environmental matrices. PMID:24745740

  1. Determination of nitrated phenolic compounds in rain by liquid chromatography/atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Kohler, Martin; Heeb, Norbert V

    2003-07-01

    A sensitive, specific, and rapid analytical method based on liquid-liquid extraction and liquid chromatography/atmospheric pressure chemical ionization mass spectrometry has been developed for trace analysis of nitrated phenolic compounds in rain samples. Selective detection in the low nanogram-per-milliliter range was achieved on the basis of selected ion monitoring of the respective phenolate anions [M - H]-. The presence of alkylated (C1-C3) and nonalkylated nitrophenols (C0) was confirmed by their characteristic neutral loss of nitrogen dioxide upon collision-induced dissociation in tandem mass spectrometry mode. In individual rain samples, 27 C0-C3-nitrophenol isomers as well as 16 C0-C3-dinitrophenol isomers were detected. Total levels of nitro- and dinitrophenol isomers were estimated on the basis of 2-nitrophenol and 2,6-dinitrophenol. Concentrations between 0.66 and 2.0, 12-29, 12-36, and 5.5-12 microg/L were obtained for the C0-, C1-, C2-, and C3-nitrophenols, respectively. Lower levels of 0.19-1.4, 0.39-2.1, 0.053-0.55, and 0.081-0.10 microg/L were estimated for the corresponding C0-, C1-, C2-, and C3-dinitrophenols. The highest number of individual isomers was found in winter rain samples, and distinctive isomeric patterns were observed for individual samples. Mono- and dialkylated nitrophenols and non- and monoalkylated dinitrophenols represent the major part of nitro- and dinitrophenol species. Comparing the pattern of Co-, C1-, and C2-nitrophenols in rain with the corresponding Co-, C1-, and C2-benzene pattern in ambient air suggests that atmospheric oxidation and nitration processes of alkylbenzenes are favored, as compared to those of benzene. PMID:12964759

  2. Chemical and photochemical water oxidation catalyzed by mononuclear ruthenium complexes with a negatively charged tridentate ligand.

    PubMed

    Duan, Lele; Xu, Yunhua; Gorlov, Mikhail; Tong, Lianpeng; Andersson, Samir; Sun, Licheng

    2010-04-19

    Two mononuclear ruthenium complexes [RuL(pic)3] (1) and [RuL(bpy)(pic)] (2) (H2L = 2,6-pyridinedicarboxylic acid, pic = 4-picoline, bpy =2,2'-bipyridine) have been synthesized and fully characterized. Both complexes could promote water oxidation chemically and photochemically. Compared with other known ruthenium-based water oxidation catalysts using [Ce(NH4)2(NO3)6] (Ce(IV)) as the oxidant in solution at pH?1.0, complex 1 is one of the most active catalysts yet reported with an initial rate of 0.23?turnover?s(-1). Under acidic conditions, the equatorial 4-picoline in complex 1 dissociates first. In addition, ligand exchange in 1 occurs when the Ru(III) state is reached. Based on the above observations and MS measurements of the intermediates during water oxidation by 1 using Ce(IV) as oxidant, [RuL(pic)2(H2O)](+) is proposed as the real water oxidation catalyst. PMID:20229528

  3. Computational and Experimental Assessment of Benzene Cation Chemistry for the Measurement of Marine Derived Biogenic Volatile Organic Compounds with Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zoerb, M.; Kim, M.; Zimmermann, K.; Bertram, T. H.

    2013-12-01

    Chemical ionization mass spectrometry (CIMS) is a highly selective and sensitive technique for the measurement of trace gases in the atmosphere. However, competing side reactions and dependence on relative humidity (RH) can make the transition from the laboratory to the field challenging. Effective implementation of chemical ionization requires a thorough knowledge of the elementary steps leading to ionization of the analyte. We have recently investigated benzene cations for the detection of marine derived biogenic volatile organic compounds (BVOCs), such isoprene and terpene compounds, from algal bloom events. Our experimental results indicate that benzene ion chemistry is an attractive candidate for field measurements, and the RH dependence is weak. To further understand the advantages and limitations of this approach, we have also used electronic structure theory calculations to compliment the experimental work. These theoretical methods can provide valuable insight into the physical chemistry of ion molecule reactions including thermodynamical information, the stability of ions to fragmentation, and potential sources of interference such as dehydration to form isobaric ions. The combined experimental and computational approach also allows validation of the theoretical methods and will provide useful information towards gaining predictive power for the selection of appropriate reagent ions for future experiments.

  4. CuFe2O4 magnetic nanocrystal clusters as a matrix for the analysis of small molecules by negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Lin, Zian; Zheng, Jiangnan; Bian, Wei; Cai, Zongwei

    2015-07-13

    CuFe2O4 magnetic nanocrystal clusters (CuFe2O4 MNCs) were proposed as a new matrix for small molecule analysis by negative ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) for the first time. We demonstrated its advantages over conventional organic matrices in the detection of small molecules such as amino acids, peptides, nucleobases, fatty acids, and steroid hormones. A systematic comparison of CuFe2O4 MNCs with different ionization modes revealed that MS spectra obtained for the CuFe2O4 MNC matrix in the negative ion mode was only featured by deprotonated ion peaks with a free matrix background, which was different from the complicated alkali metal adducts produced in the positive ion mode. The developed method was found relatively tolerant to salt contamination and exhibited good reproducibility. A detection limit down to the subpicomolar level was achieved when testosterone was analyzed. In addition, by comparison of the MS spectra obtained from bare Fe3O4 and MFe2O4 MNC (M = Co, Ni, Cu, Zn) matrices, two main factors of MFe2O4 MNC matrices were revealed to play a vital role in assisting the negative ion desorption/ionization (D/I) process: doping transition metals into ferrite nanocrystals favoring laser absorption and energy transfer and a good match between the UV absorption of MFe2O4 MNCs and the excitation of nitrogen laser source facilitating LDI efficiency. This work creates a new branch of application for MFe2O4 MNCs and provides an alternative solution for small molecule analysis. PMID:26086699

  5. Differentiation of Positional Isomers of Hybrid Peptides Containing Repeats of ?-Nucleoside Derived Amino Acid (?-Nda-) and L-Amino Acids by Positive and Negative Ion Electrospray Ionization Tandem Mass Spectrometry (ESI-MS n )

    Microsoft Academic Search

    B. Raju; M. Ramesh; R. Srinivas; S. Chandrasekhar; N. Kiranmai; V. U. M. Sarma

    2011-01-01

    A new class of positional isomeric pairs of -Boc protected oligopeptides comprised of alternating nucleoside derived ?-amino\\u000a acid (?-Nda-) and L-amino acid residues (alanine, valine, and phenylalanine) have been differentiated by both positive and\\u000a negative ion electrospray ionization ion-trap tandem mass spectrometry (ESI-MS\\u000a n\\u000a ). The protonated dipeptide positional isomers with ?-Nda- at the N-terminus lose CH3OH, NH3, and C2H4O2,

  6. Differentiation of regioisomeric aromatic ketocarboxylic acids by atmospheric pressure chemical ionization CAD tandem mass spectrometry in a linear quadrupole ion trap mass spectrometer

    SciTech Connect

    Amundson, Lucas M.; Owen, Ben C.; Gallardo, Vanessa A.; Habicht, S. C.; Fu, M.; Shea, R. C.; Mossman, A. B.; Kenttämaa, Hilkka I.

    2011-01-01

    Positive-mode atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS n ) was tested for the differentiation of regioisomeric aromatic ketocarboxylic acids. Each analyte forms exclusively an abundant protonated molecule upon ionization via positive-mode APCI in a commercial linear quadrupole ion trap (LQIT) mass spectrometer. Energy-resolved collision-activated dissociation (CAD) experiments carried out on the protonated analytes revealed fragmentation patterns that varied based on the location of the functional groups. Unambiguous differentiation between the regioisomers was achieved in each case by observing different fragmentation patterns, different relative abundances of ion-molecule reaction products, or different relative abundances of fragment ions formed at different collision energies. The mechanisms of some of the reactions were examined by H/D exchange reactions and molecular orbital calculations.

  7. Chemical composition of single aerosol particles at Idaho Hill: Positive ion measurements

    Microsoft Academic Search

    D. M. Murphy; D. S. Thomson

    1997-01-01

    The chemical compositions of single aerosol particles larger than 0.3 gm optical diameter were measured at Idaho Hill using a laser ionization mass spectrometer. The mass spectrometer can analyze either positive or negative ions; this paper covers the negative ion results. Sulfate, nitrate, organics, O-, and OH- were the most common peaks observed in the negative ion spectra. Other species

  8. Comparison of electron impact, desorption, chemical ionization, field desorption, and fast atom bombardment mass spectra of nine monosubstituted group VI metal carbonyls

    SciTech Connect

    van Breemen, R.B.; Martin, L.B.; Schreiner, A.F.

    1988-07-01

    Nine monosubstituted group VI metal pentacarbonyls of the type M(CO)/sub 5/L (where M = Cr, Mo, or W; and L = P(C/sub 6/H/sub 5/)/sub 3/, As(C/sub 6/H/sub 5/)/sub 3/, or Sb(C/sub 6/H/sub 5/)/sub 3/) were synthesized and purified by recrystallization so that they contained no unbound ligands, excess reagents, or other contaminants as measured by high-performance liquid chromatography. Positive ion mass spectra were obtained by electron impact (EI), desorption chemical ionization (DCI), field desorption (FD), and fast atom bombardment (FAB) mass spectrometry. B/E linked scanning was used to confirm the fragmentation pathway in FAB mass spectra. While all four ionization methods formed molecular ions, M/sup +/, the desorption ionization methods tended to produce more abundant molecular ions than EI. FD, for instance, formed molecular ions without any fragmentation. The most abundant fragment ions of the ligand (L) were observed with DCI. FAB spectra contained abundant molecular ions and extensive structural information in ion fragments.

  9. Matrix Assisted Ionization: New Aromatic and Nonaromatic Matrix Compounds Producing Multiply Charged Lipid, Peptide, and Protein Ions in the Positive and Negative Mode Observed Directly from Surfaces

    NASA Astrophysics Data System (ADS)

    Li, Jing; Inutan, Ellen D.; Wang, Beixi; Lietz, Christopher B.; Green, Daniel R.; Manly, Cory D.; Richards, Alicia L.; Marshall, Darrell D.; Lingenfelter, Steven; Ren, Yue; Trimpin, Sarah

    2012-10-01

    Matrix assisted inlet ionization (MAII) is a method in which a matrix:analyte mixture produces mass spectra nearly identical to electrospray ionization without the application of a voltage or the use of a laser as is required in laserspray ionization (LSI), a subset of MAII. In MAII, the sample is introduced by, for example, tapping particles of dried matrix:analyte into the inlet of the mass spectrometer and, therefore, permits the study of conditions pertinent to the formation of multiply charged ions without the need of absorption at a laser wavelength. Crucial for the production of highly charged ions are desolvation conditions to remove matrix molecules from charged matrix:analyte clusters. Important factors affecting desolvation include heat, vacuum, collisions with gases and surfaces, and even radio frequency fields. Other parameters affecting multiply charged ion production is sample preparation, including pH and solvent composition. Here, findings from over 100 compounds found to produce multiply charged analyte ions using MAII with the inlet tube set at 450 °C are presented. Of the compounds tested, many have -OH or -NH2 functionality, but several have neither (e.g., anthracene), nor aromaticity or conjugation. Binary matrices are shown to be applicable for LSI and solvent-free sample preparation can be applied to solubility restricted compounds, and matrix compounds too volatile to allow drying from common solvents. Our findings suggest that the physical properties of the matrix such as its morphology after evaporation of the solvent, its propensity to evaporate/sublime, and its acidity are more important than its structure and functional groups.

  10. Volume 182, number 3,1 CHEMICAL PHYSICS LETTERS 2 August 1991 Photoelectrons from resonant ionization of Na,

    E-print Network

    Berry, R. Stephen

    ionization of Na,: angular and non-Franck-Condon energy distributions Robert G. Daniel, James S. Keller, Dina Pines and R. Stephen Berry TheDepartmenl ofChemiwy and James Franck Institute, Chicago, IL 60637, USA the B state do not correspond to Franck-Condon distributions, according to the photoelectron energy

  11. [Determination of short chain chlorinated paraffins in polyvinyl chloride plastics by gas chromatography-negative chemical ion/mass spectrometry].

    PubMed

    Xing, Yuanna; Lin, Zhihui; Feng, Anhong; Wang, Xin; Gong, Yemeng; Chen, Zeyong

    2015-02-01

    A novel method was established to determine short chain chlorinated paraffins (SC-CPs) in polyvinyl chloride (PVC) plastics by gas chromatography-negative chemical ion/mass spectrometry (GC-NCI/MS). Ultrasonic extraction was used to extract SCCPs from PVC plastics. The optimal extraction time was 1.5 h, and concentrated sulfuric acid was adopted to purify the extracted solution. Finally, SCCPs in a sample were detected by GC-NCI/MS at 160 C and with methane reagent gas at 1. 5 mL/min. This method was not influenced by medium chain chlorinated paraffins (MCCPs) in the sample, and accurate quantitation was made for SCCPs. Twelve batches of samples were analyzed and SCCPs were detected in each batch with the contents from 0. 3 x 10(2)mg/kg to 3. 5 x 10(4)mg/kg. With respect to European limitation of SC-CPs (1%), four batches of samples did not comply with the European regulation, and they accounted for 33. 3%. Obviously, high SCCPs risk was presented in PVC plastics. PMID:25989692

  12. Comparison Of Quantum Mechanical And Classical Trajectory Calculations Of Cross Sections For Ion-Atom Impact Ionization of Negative - And Positive -Ions For Heavy Ion Fusion Applications

    SciTech Connect

    Igor D. Kaganovich; Edward A. Startsev; Ronald C. Davidson

    2003-05-15

    Stripping cross sections in nitrogen have been calculated using the classical trajectory approximation and the Born approximation of quantum mechanics for the outer shell electrons of 3.2GeV I{sup -} and Cs{sup +} ions. A large difference in cross section, up to a factor of six, calculated in quantum mechanics and classical mechanics, has been obtained. Because at such high velocities the Born approximation is well validated, the classical trajectory approach fails to correctly predict the stripping cross sections at high energies for electron orbitals with low ionization potential.

  13. Chemical profiling of the Chinese herb formula Xiao-Cheng-Qi Decoction using liquid chromatography coupled with electrospray ionization mass spectrometry.

    PubMed

    Zhao, Hai-Yu; Fan, Miao-Xuan; Wu, Xu; Wang, Hong-Jie; Yang, Jian; Si, Nan; Bian, Bao-Lin

    2013-03-01

    An approach was established to analyze the chemical profiling of Xiao-Cheng-Qi Decoction (XCQD) using liquid chromatography coupled with electrospray ionization tandem mass spectrometry. XCQD consisted of three herbal medicines (Rhubarb, Fructus Aurantii Immaturus and Cortex Magnoliae Officinalis). The traditional water extractive method was applied in the sample preparation, which was identical with clinical use. The characteristic fragmentation pathways of 17 reference compounds were comprehensively studied, including precursors of tannins, flavonones, anthraquinones and lignan. In total, 71 constituents were identified or tentatively characterized based on their mass spectrometry fragmentations and chromatographic behaviors. By comparing their relative contents, flavanones and anthraquinones were supposed to be used together for the quality control of XCQD. Further pharmacology and pharmacokinetics investigations should be performed on the basis of the present chemical profiling study. PMID:22977122

  14. Li-doping process for Li xSiO-negative active material synthesized by chemical method for lithium-ion cells

    NASA Astrophysics Data System (ADS)

    Tabuchi, Toru; Yasuda, Hideo; Yamachi, Masanori

    Li-doped SiO-negative active material (Li xSiO) has been successfully synthesized by chemical method with immersion in Li-organic complex solution obtained by dissolving naphthalene and metallic Li into butyl methyl ether (BME) solvent. The rest potential of resultant Li xSiO electrode drastically shifts to less noble value at the beginning of immersion and tends to be stable at around 0.21 V versus Li/Li +, which means the progress of Li-doping into SiO-negative active material. Furthermore, this chemical Li-doping process proceeds by the catalysis function of naphthalene and leads to reduce the irreversible capacity of SiO-negative electrode caused by consumption of Li sources provided from positive electrode.

  15. Determination of polycyclic aromatic hydrocarbons in fractions in asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

    2015-07-01

    An analytical method using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization for the determination of polycyclic aromatic hydrocarbons in asphalt fractions has been developed. The 14 compounds determined, characterized by having two or more condensed aromatic rings, are expected to be present in asphalt and are considered carcinogenic and mutagenic. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all of the compounds. The limits of detection ranged from 0.5 to 346.5 ?g/L and the limits of quantification ranged from 1.7 to 1550 ?g/L. The method was validated against a diesel particulate extract standard reference material (NIST SRM 1975), and the obtained concentrations agreed with the certified values. The method was applied to asphalt samples after its fractionation according to ASTM D4124 and the method of Green. The concentrations of the seven polycyclic aromatic hydrocarbons quantified in the sample ranged from 0.86 mg/kg for benzo[ghi]perylene to 98.32 mg/kg for fluorene. PMID:25885756

  16. Direct correlation of the crystal structure of proteins with the maximum positive and negative charge states of gaseous protein ions produced by electrospray ionization

    Microsoft Academic Search

    Halan Prakash; Shyamalava Mazumdar

    2005-01-01

    Electrospray mass spectrometric studies in native folded forms of several proteins in aqueous solution have been performed\\u000a in the positive and negative ion modes. The mass spectra of the proteins show peaks corresponding to multiple charge states\\u000a of the gaseous protein ions. The results have been analyzed using the known crystal structures of these proteins. Crystal\\u000a structure analysis shows that

  17. Structural Characterization of ?,?-Unsaturated Aldehydes by GC\\/MS is Dependent upon Ionization Method

    Microsoft Academic Search

    Eric K. Long; Irina Smoliakova; Ales Honzatko; Matthew J. Picklo Sr

    2008-01-01

    ?,?-unsaturated aldehydes are toxic products of lipid peroxidation. Detection and characterization of these aldehydes is important\\u000a in many human disease states as well as in the food industry. Our study shows that electron ionization-mass spectrometry (EI-MS)\\u000a and positive-ion chemical ionization-mass spectrometry (PICI-MS), but not electron capture negative ionization-mass spectrometry\\u000a (ECNI-MS), can be used to detect the C4-hydroxylation state of ?,?-unsaturated

  18. Identification of N-gluconyl [corrected] ethanolamine in wine by negative electrospray ionization with post-column chloride attachment and accurate mass determination on a triple-quadrupole mass spectrometer.

    PubMed

    de Rijke, Eva; Bouter, Nico; Ruisch, Bart J; Haiber, Stephan; König, Thorsten

    2007-07-13

    In this study a specific taste modulating flavour-ingredient, N-gluconyl [corrected] ethanolamine, was determined in two Beerenauslese wines using two different LC-MS techniques. For a first screening LC-MS(2) on an ion-trap mass spectrometer with negative electrospray ionization (ESI(-)) was applied. Sensitivity (and selectivity) was successfully increased approx. 10-fold by post-column addition of chloroform to form [M+Cl](-) species. In a second step LC-MS(2) on a triple-quadrupole mass spectrometer in accurate mass mode confirmed the presence of N-gluconyl [corrected] ethanolamine in wine. The application of the right MS(2) transitions for an unambiguous identification is discussed. N-Gluconyl [corrected] ethanolamine concentrations in the wines were found to be 1.1 and 4.0 microg/l. PMID:17222856

  19. Resonance enhanced multiphoton ionization probing of H atoms and CH3 radicals in a hot lament chemical vapour deposition reactor

    E-print Network

    Bristol, University of

    hot ®lament (HF) reactor, or plasma (e.g. microwave) enhanced. The formation of H atoms chemical vapour deposition reactor James A. Smith, Moray A. Cook, Stephen R. Langford, Stephen A. Redman reactor used for diamond chemical vapour deposition (CVD). Parameters varied include the hydrocarbon (CH4

  20. Development of New Soft Ionization Mass Spectrometry Approaches for Spatial Imaging of Complex Chemical and Biological Systems

    E-print Network

    Chemical and Biological Systems Research Team: Julia Laskin, Ljiljana Pasa-Toli, Brandi Heath, Ingela to multiple chemical and biological systems Key Successes Developed unique tools for imaging biological world's first C60 SIMS FT-ICR MS. Unique capabilities for imaging biological samples: High mass accuracy

  1. Enhanced Nicotine Metabolism in HIV-1–Positive Smokers Compared with HIV-Negative Smokers: Simultaneous Determination of Nicotine and its Four Metabolites in Their Plasma Using a Simple and Sensitive Electrospray Ionization Liquid Chromatography–Tandem Mass Spectrometry Technique

    PubMed Central

    Earla, Ravinder; Ande, Anusha; McArthur, Carole; Kumar, Anil

    2014-01-01

    Smoking is approximately three times more prevalent in HIV-1–positive than HIV-negative individuals in the United States. Nicotine, which is the major constituent of tobacco, is rapidly metabolized mainly by cytochrome P450 (CYP2A6) to many metabolites. In this study, we developed a simple, fast, and sensitive electrospray ionization liquid chromatography–tandem mass spectrometry method using a strong cation solid phase extraction, and determined the concentration of nicotine and its four major metabolites (cotinine, nornicotine, norcotinine, and trans-3?-hydroxycotinine) in the plasma of HIV-1–positive and HIV-negative smokers. The multiple reaction monitoring transitions for nicotine, cotinine, trans-3?-hydroxycotinine, nornicotine, norcotinine, nicotine-d4, and cotinine-d3 were selected at mass-to-charge ratios of 163.3/117.1, 177.5/80.3, 193.2/80.1, 149.5/132.3, 163.4/80.3, 167.3/121.4, and 180.3/101.2, respectively. The lower limit of quantitation for nicotine and its metabolites was 0.53 ng/ml, which is relatively more sensitive than those previously reported. The concentration of nicotine was detected 5-fold lower in HIV-1–positive smokers (7.17 ± 3.8 ng/ml) than that observed in HIV-negative smokers (33.29 ± 15.4 ng/ml), whereas the concentration of the metabolite nornicotine was 3-fold higher in HIV-1–positive smokers (6.8 ± 2.9 ng/ml) than in HIV-negative smokers (2.3 ± 1.2 ng/ml). Although it was statistically nonsignificant, the concentration of the metabolite cotinine was also higher in HIV-1–positive smokers (85.6 ± 60.5 ng/ml) than in HIV-negative smokers (74.9 ± 40.5 ng/ml). In conclusion, a decrease in the concentration of nicotine and an increase in the concentration of its metabolites in HIV-1–positive smokers compared with HIV-negative smokers support the hypothesis that nicotine metabolism is enhanced in HIV-1–positive smokers compared with HIV-negative smokers. PMID:24301609

  2. Systematic chemical profiling of a multicomponent Chinese herbal formula Huo Luo Xiao Ling Dan by ultra high performance liquid chromatography coupled with electrospray ionization quadrupoletime-of-flight mass spectrometry.

    PubMed

    Wang, Fenrong; Ai, Yu; Wu, Yun; Ma, Wen; Bian, Qiaoxia; Lee, David Y-W; Dai, Ronghua

    2015-03-01

    Huo Luo Xiao Ling Dan, a Chinese herbal formula consisting of 11 different herbs, has been used in folk medicine for the treatment of arthritis and other chronic inflammatory diseases. However, the chemical compositions of Huo Luo Xiao Ling Dan are not completely characterized. In the present study, an ultra high performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight mass spectrometry method in positive and negative ion modes was employed to identify biochemical constitutes in Huo Luo Xiao Ling Dan. As a result, a total of 76 compounds including alkaloids, monoterpene glycosides, iridoids, phenolic acids, and tanshinones, coumarins, lactones, flavones, and their glycosides, triterpenes, and triterpene saponins were characterized by comparing the retention time and mass spectrometry data with reference standards within 5 ppm error or by reference to the reference literature. These results would provide the basis for a further in vivo study of Huo Luo Xiao Ling Dan and information for potential new drug candidates for treating arthritis and other chronic inflammatory diseases. PMID:25641883

  3. Organic chemical analysis on a microscopic scale using two-step laser desorption/laser ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kovalenko, L. J.; Philippoz, J.-M.; Bucenell, J. R.; Zenobi, R.; Zare, R. N.

    1991-04-01

    The distribution of PAHs in the Allende meteorite has been measured using two-step laser desorption and laser multiphoton-ionization mass spectrometry. This method enables in situ analysis (with a spatial resolution of 1 mm or better) of selected organic molecules. Results show that PAH concentrations are locally high compared to the average concentration found by analysis of pulverized samples, and are found primarily in the fine-grained matrix; no PAHs were detected in the interiors of individual chondrules at the detection limit (about 0.05 ppm).

  4. Application of high resolution Chemical Ionization Mass Spectrometry (CI-ToFMS) to study SOA composition: focus on formation of oxygenated species via aqueous phase processing

    NASA Astrophysics Data System (ADS)

    Aljawhary, D.; Lee, A. K. Y.; Abbatt, J. P. D.

    2013-07-01

    This paper demonstrates the capabilities of Chemical Ionization Mass Spectrometry (CIMS) to study secondary organic aerosol (SOA) composition with a high resolution (HR) time-of-flight mass analyzer (aerosol-CI-ToFMS). In particular, by studying aqueous oxidation of Water Soluble Organic Compounds (WSOC) extracted from ?-pinene ozonolysis SOA, we assess the capabilities of three common CIMS reagent ions: (a) protonated water clusters (H2O)nH+, (b) acetate CH3C(O)O- and (c) iodide water clusters I(H2O)n- to monitor SOA composition. As well, we report the relative sensitivity of these reagent ions to a wide range of common organic aerosol constituents. We find that (H2O)nH+ is more selective to the detection of less oxidized species, so that the range of O/C and OSC (carbon oxidation state) in the SOA spectra is considerably lower than those measured using CH3C(O)O- and I(H2O)n-. Specifically, (H2O)nH+ ionizes organic compounds with OSC ? 1.3, whereas CH3C(O)O- and I(H2O)n- both ionize highly oxygenated organics with OSC up to 4 with I(H2O)n- being more selective towards multi-functional organic compounds. In the bulk O/C and H/C space, i.e. in a Van Krevelen plot, there is a remarkable agreement in both absolute magnitude and oxidation trajectory between CI-ToFMS data and those from a high resolution aerosol mass spectrometer (HR-AMS). This indicates that the CI-ToFMS data captures much of the chemical change occurring in the particle and that gas phase species, which are not detected by the HR-AMS, do not dominate the overall ion signal. Finally, the data illustrate the capability of aerosol-CI-ToFMS to monitor specific chemical change, including the fragmentation and functionalization reactions that occur during organic oxidation, and the oxidative conversion of dimeric SOA species into monomers. Overall, aerosol-CI-ToFMS is a valuable, selective complement to some common SOA characterization methods, such as AMS and spectroscopic techniques. Both laboratory and ambient SOA samples can be analyzed using the techniques illustrated in the paper.

  5. Physico-Chemical-Managed Killing of Penicillin-Resistant Static and Growing Gram-Positive and Gram-Negative Vegetative Bacteria

    NASA Technical Reports Server (NTRS)

    Richmond, Robert Chaffee (Inventor); Schramm, Jr., Harry F. (Inventor); Defalco, Francis G. (Inventor); Farris, III, Alex F. (Inventor)

    2012-01-01

    Systems and methods for the use of compounds from the Hofmeister series coupled with specific pH and temperature to provide rapid physico-chemical-managed killing of penicillin-resistant static and growing Gram-positive and Gram-negative vegetative bacteria. The systems and methods represent the more general physico-chemical enhancement of susceptibility for a wide range of pathological macromolecular targets to clinical management by establishing the reactivity of those targets to topically applied drugs or anti-toxins.

  6. Chemical vapor deposition of aminopropyl silanes in microfluidic channels for highly efficient microchip capillary electrophoresis-electrospray ionization-mass spectrometry.

    PubMed

    Batz, Nicholas G; Mellors, J Scott; Alarie, Jean Pierre; Ramsey, J Michael

    2014-04-01

    We describe a chemical vapor deposition (CVD) method for the surface modification of glass microfluidic devices designed to perform electrophoretic separations of cationic species. The microfluidic channel surfaces were modified using aminopropyl silane reagents. Coating homogeneity was inferred by precise measurement of the separation efficiency and electroosmotic mobility for multiple microfluidic devices. Devices coated with (3-aminopropyl)di-isopropylethoxysilane (APDIPES) yielded near diffusion-limited separations and exhibited little change in electroosmotic mobility between pH 2.8 and pH 7.5. We further evaluated the temporal stability of both APDIPES and (3-aminopropyl)triethoxysilane (APTES) coatings when stored for a total of 1 week under vacuum at 4 °C or filled with pH 2.8 background electrolyte at room temperature. Measurements of electroosmotic flow (EOF) and separation efficiency during this time confirmed that both coatings were stable under both conditions. Microfluidic devices with a 23 cm long, serpentine electrophoretic separation channel and integrated nanoelectrospray ionization emitter were CVD coated with APDIPES and used for capillary electrophoresis (CE)-electrospray ionization (ESI)-mass spectrometry (MS) of peptides and proteins. Peptide separations were fast and highly efficient, yielding theoretical plate counts over 600,000 and a peak capacity of 64 in less than 90 s. Intact protein separations using these devices yielded Gaussian peak profiles with separation efficiencies between 100,000 and 400,000 theoretical plates. PMID:24655020

  7. Comprehensive chemical characterization of Rapé tobacco products: Nicotine, un-ionized nicotine, tobacco-specific N'-nitrosamines, polycyclic aromatic hydrocarbons, and flavor constituents.

    PubMed

    Stanfill, Stephen B; Oliveira da Silva, André Luiz; Lisko, Joseph G; Lawler, Tameka S; Kuklenyik, Peter; Tyx, Robert E; Peuchen, Elizabeth H; Richter, Patricia; Watson, Clifford H

    2015-08-01

    Rapé, a diverse group of smokeless tobacco products indigenous to South America, is generally used as a nasal snuff and contains substantial amount of plant material with or without tobacco. Previously uncharacterized, rapé contains addictive and harmful chemicals that may have public health implications for users. Here we report % moisture, pH, and the levels of total nicotine, un-ionized nicotine, flavor-related compounds, tobacco-specific N-nitrosamines (TSNAs) and polycyclic aromatic hydrocarbons (PAHs) for manufactured and hand-made rapé. Most rapé products were mildly acidic (pH 5.17-6.23) with total nicotine ranging from 6.32 to 47.6 milligram per gram of sample (mg/g). Calculated un-ionized nicotine ranged from 0.03 to 18.5?mg/g with the highest values associated with hand-made rapés (pH 9.75-10.2), which contain alkaline ashes. In tobacco-containing rapés, minor alkaloid levels and Fourier transform infrared spectra were used to confirm the presence of Nicotiana rustica, a high nicotine tobacco species. There was a wide concentration range of TSNAs and PAHs among the rapés analyzed. Several TSNAs and PAHs identified in the products are known or probable carcinogens according to the International Agency for Research on Cancer. Milligram quantities of some non-tobacco constituents, such as camphor, coumarin, and eugenol, warrant additional evaluation. PMID:25934468

  8. Unusual mechanism for H{sub 3}{sup +} formation from ethane as obtained by femtosecond laser pulse ionization and quantum chemical calculations

    SciTech Connect

    Kraus, Peter M.; Schwarzer, Martin C.; Schirmel, Nora; Urbasch, Gunter; Frenking, Gernot; Weitzel, Karl-Michael [Fachbereich Chemie, Physikalische Chemie, Philipps-Universitaet Marburg, Hans-Meerwein-Strasse, D-35032 Marburg (Germany)

    2011-03-21

    The formation of H{sub 3}{sup +} from saturated hydrocarbon molecules represents a prototype of a complex chemical process, involving the breaking and the making of chemical bonds. We present a combined theoretical and experimental investigation providing for the first time an understanding of the mechanism of H{sub 3}{sup +} formation at the molecular level. The experimental approach involves femtosecond laser pulse ionization of ethane leading to H{sub 3}{sup +} ions with kinetic energies on the order of 4 to 6.5 eV. The theoretical approach involves high-level quantum chemical calculation of the complete reaction path. The calculations confirm that the process takes place on the potential energy surface of the ethane dication. A surprising result of the theoretical investigation is, that the transition state of the process can be formally regarded as a H{sub 2} molecule attached to a C{sub 2}H{sub 4}{sup 2+} entity but IRC calculations show that it belongs to the reaction channel yielding C{sub 2}H{sub 3}{sup +}+ H{sub 3}{sup +}. Experimentally measured kinetic energies of the correlated H{sub 3}{sup +} and C{sub 2}H{sub 3}{sup +} ions confirm the reaction path suggested by theory.

  9. Determination of metformin in mouse, rat, dog and human plasma samples by laser diode thermal desorption/atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

    Swales, John G; Gallagher, Richard; Peter, Raimund M

    2010-11-01

    A simple, rapid and robust high-throughput assay for the quantitative analysis of metformin in plasma from different species using laser diode thermal desorption interfaced with atmospheric chemical pressure ionization tandem mass spectrometry (LDTD-APCI-MSMS) was developed for use in a pharmaceutical discovery environment. In order to minimize sample preparation a generic protein precipitation method was used to extract metformin from the plasma. Laser diode thermal desorption is a relatively new sample introduction method, the optimization of the instrumental parameters are presented. The method was successfully applied to spiked mouse, rat, dog and human plasma samples and was subsequently used to determine the oral pharmacokinetics of metformin after dosing to male rats in order to support drug discovery projects. The deviations for intra-assay accuracy and precision across the four species were less than 30% at all calibration and quality control levels. PMID:20547025

  10. Sulfur dioxide measurements in the lower, middle and upper troposphere: Deployment of an aircraft-based chemical ionization mass spectrometer with permanent in-flight calibration

    NASA Astrophysics Data System (ADS)

    Speidel, M.; Nau, R.; Arnold, F.; Schlager, H.; Stohl, A.

    Measurements of atmospheric SO 2 have been made at altitudes between ground level and 12 km in the lower, middle and upper troposphere. The measurements were carried out within the framework of the ITOP (Intercontinental Transport of Ozone and Precursors) campaign in summer 2004 above Europe and the Eastern Atlantic. They were made using a novel very sensitive and fast-response aircraft-based ion trap CIMS instrument (ITCIMS; CIMS=chemical ionization mass spectrometry), which was continuously calibrated using isotopically labelled SO 2. During a total of eight flights of the research aircraft FALCON (DLR) air masses of different origin and different degree of pollution, indicated by measured elevated atmospheric SO 2 mole fractions, were intercepted. Often elevated concentrations of SO 2, which stemmed from North America were observed over Europe and the eastern Atlantic.

  11. Preparative mass-spectrometry profiling of bioactive metabolites in Saudi-Arabian propolis fractionated by high-speed countercurrent chromatography and off-line atmospheric pressure chemical ionization mass-spectrometry injection.

    PubMed

    Jerz, Gerold; Elnakady, Yasser A; Braun, André; Jäckel, Kristin; Sasse, Florenz; Al Ghamdi, Ahmad A; Omar, Mohamed O M; Winterhalter, Peter

    2014-06-20

    Propolis is a glue material collected by honeybees which is used to seal cracks in beehives and to protect the bee population from infections. Propolis resins have a long history in medicinal use as a natural remedy. The multiple biological properties are related to variations in their chemical compositions. Geographical settings and availability of plant sources are important factors for the occurrence of specific natural products in propolis. A propolis ethylacetate extract (800mg) from Saudi Arabia (Al-Baha region) was separated by preparative scale high-speed countercurrent chromatography (HSCCC) using a non-aqueous solvent system n-hexane-ACN (1:1, v/v). For multiple metabolite detection, the resulting HSCCC-fractions were sequentially injected off-line into an atmospheric pressure chemical ionization mass-spectrometry (APCI-MS/MS) device, and a reconstituted mass spectrometry profile of the preparative run was visualized by selected ion traces. Best ion-intensities for detected compounds were obtained in the negative APCI mode and monitored occurring co-elution effects. HSCCC and successive purification steps resulted in the isolation and characterization of various bioactive natural products such as (12E)- and (12Z)-communic acid, sandaracopimaric acid, (+)-ferruginol, (+)-totarol, and 3?-acetoxy-19(29)-taraxasten-20a-ol using EI-, APCI-MS and 1D/2D-NMR. Cycloartenol-derivatives and triterpene acetates were isolated in mixtures and elucidated by EI-MS and 1D-NMR. Free fatty acids, and two labdane fatty acid esters were identified by APCI-MS/MS. In total 19 metabolites have been identified. The novel combination of HSCCC fractionation, and APCI-MS-target-guided molecular mass profiling improve efficiency of lead-structure identification. PMID:24831423

  12. Surface-activated chemical ionization ion trap mass spectrometry for the analysis of cocaine and benzoylecgonine in hair after extraction and sample dilution.

    PubMed

    Cristoni, Simone; Basso, Elisa; Gerthoux, Piermario; Mocarelli, Paolo; Gonella, Elisabetta; Brambilla, Maura; Crotti, Sara; Bernardi, Luigi Rossi

    2007-01-01

    Surface-activated chemical ionization (SACI) was employed for the analysis of cocaine and its metabolite, benzoylecgonine, extracted from hair. Following decontamination and acid hydrolysis procedures on the hair sample, the sample solution was diluted (1:10) and directly analyzed by liquid chromatography/surface-activated chemical ionization multiple collisional stage single reaction monitoring mass spectrometry (LC/SACI-MS(3)-SRM) without solid-phase extraction (SPE) pre-purification and concentration procedures. To increase the selectivity of the method, MS(3) was chosen instead of the less selective MS/MS. This data was compared with that achieved using gas chromatography/mass spectrometry (GC/MS), the reference method used by the Italian Government Institute of Health protocol. The limits of detection (LODs) were 0.003 ng/(mg hair) for cocaine and 0.02 ng/(mg hair) for benzoylecgonine and the limits of quantitation (LOQs) were 0.01 ng/(mg hair) for cocaine and 0.04 ng/(mg hair) for benzoylecgonine. The squared correlation coefficient (R(2)) of the calibration curve was 0.9887-0.9980 for cocaine and 0.9987-0.9997 for benzoylecgonine. The percent accuracy error was 2-5% for both cocaine and benzoylecgonine using the LC/SACI-MS(3)-SRM approach, whereas it was higher for benzoylecgonine (20-25%) using the LC/SACI-MS/MS-SRM approach compared with the GC/MS data due to hair matrix contamination. In both cases, high precision was achieved (1-3% precision error), which confirmed the stability of the developed methods. PMID:17610217

  13. XIV International Conference on Atmospheric Electricity, August 08-12, 2011, Rio de Janeiro, Brazil How Photo-ionization and Background Ionization

    E-print Network

    Ebert, Ute

    conclusions on the importance of photo- ionization and background ionization for streamers in atmospheric air-ionization or background ionization. Background ionization in the form of negative ions can come from ionization generated to the needle electrode. Pressure is 200 mbar, temperature is room temperature. Figure reproduced from #12;XIV

  14. Evidence for an N-methyl transfer reaction in phosphatidylcholines with a terminal aldehyde during negative electrospray ionization tandem mass spectrometry.

    PubMed

    Almstrand, Ann-Charlotte; Johnson, Christopher; Murphy, Robert C

    2015-07-01

    Lipidomic analysis of the complex mixture of lipids isolated from biological systems can be a challenging process that often involves tandem mass spectrometry and interpretation of both precursor ions and product ions relative to the molecular structure of the lipids. Therefore, detailed understanding of the gas-phase ion chemistry occurring for each class of phospholipids is critically important for an accurate assignment of lipid structure. Some oxidized phosphatidylcholines are known to be biologically active and responsible for pathological events, and are therefore important targets for detection in lipidomic studies. Modification of fatty acyl chains by oxidation may, however, change the behavior of ion formation and decomposition in the mass spectrometer. In this study, we report on the mass-spectrometric behavior of 1-palmitoyl-2-(9'-oxononanoyl)-sn-glycero-3-phosphocholine, a bioactive product of phosphatidylcholine oxidation. In addition to [M-15](-) and the acetate adduct [M+59](-), three additional adduct ions, including [M-H](-), were present in significant abundance in the negative ion electrospray mass spectrum. It was found that this unexpected [M-H](-) ion was formed by the transfer of a methyl group from the choline residue on the polar head group to the aldehyde functionality of the sn-2 substituent, resulting in a 14-Da increase in the mass of the resulting sn-2 carboxylate anion formed by collisional activation of this ion. These results suggest additional rules for understanding the gas-phase ion chemistry of aldehydic phosphatidylcholine molecular species. PMID:25736244

  15. Chemical analysis of pharmaceuticals and explosives in fingermarks using matrix-assisted laser desorption ionization/time-of-flight mass spectrometry.

    PubMed

    Kaplan-Sandquist, Kimberly; LeBeau, Marc A; Miller, Mark L

    2014-02-01

    Chemical analysis of latent fingermarks, "touch chemistry," has the potential of providing intelligence or forensically relevant information. Matrix-assisted laser desorption ionization/time-of-flight mass spectrometry (MALDI/TOF MS) was used as an analytical platform for obtaining mass spectra and chemical images of target drugs and explosives in fingermark residues following conventional fingerprint development methods and MALDI matrix processing. There were two main purposes of this research: (1) develop effective laboratory methods for detecting drugs and explosives in fingermark residues and (2) determine the feasibility of detecting drugs and explosives after casual contact with pills, powders, and residues. Further, synthetic latent print reference pads were evaluated as mimics of natural fingermark residue to determine if the pads could be used for method development and quality control. The results suggest that artificial amino acid and sebaceous oil residue pads are not suitable to adequately simulate natural fingermark chemistry for MALDI/TOF MS analysis. However, the pads were useful for designing experiments and setting instrumental parameters. Based on the natural fingermark residue experiments, handling whole or broken pills did not transfer sufficient quantities of drugs to allow for definitive detection. Transferring drugs or explosives in the form of powders and residues was successful for preparing analytes for detection after contact with fingers and deposition of fingermark residue. One downfall to handling powders was that the analyte particles were easily spread beyond the original fingermark during development. Analyte particles were confined in the original fingermark when using transfer residues. The MALDI/TOF MS was able to detect procaine, pseudoephedrine, TNT, and RDX from contact residue under laboratory conditions with the integration of conventional fingerprint development methods and MALDI matrix. MALDI/TOF MS is a nondestructive technique which provides chemical information in both the mass spectra and chemical images. PMID:24447453

  16. Photochemical Dimerization of Dibenzylideneacetone: A Convenient Exercise in [2+2] Cycloaddition Using Chemical Ionization Mass Spectrometry

    ERIC Educational Resources Information Center

    Rao, G. Nageswara; Janardhana, Chelli; Ramanathan, V.; Rajesh, T.; Kumar, P. Harish

    2006-01-01

    Chemical reactions induced by light have been utilized for synthesizing highly strained, thermodynamically unstable compounds, which are inaccessible through non-photochemical methods. Photochemical cycloaddition reactions, especially those leading to the formation of four-membered rings, constitute a convenient route to compounds that are…

  17. Health effects of occupational exposure to hazardous chemicals: a comparative assessment with notes on ionizing radiation. Executive summary. Vol. 1

    Microsoft Academic Search

    M. A. Zanetos; J. C. Warling; G. M. Marsh

    1983-01-01

    This three-part report provides quantitative estimates of the risk of cancer and other diseases among persons exposed to hazardous substances in the workplace. The risk estimates presented are based on a comprehensive review of recent epidemiologic studies. Primary emphasis was placed on studies of workers exposed to hazardous chemicals under conditions typical of a given industry over a working lifetime.

  18. Basic vapor exposure for tuning the charge state distribution of proteins in negative electrospray ionization: elucidation of mechanisms by fluorescence spectroscopy.

    PubMed

    Girod, Marion; Antoine, Rodolphe; Dugourd, Philippe; Love, Craig; Mordehai, Alex; Stafford, George

    2012-07-01

    Manipulation for simplifying or increasing the observed charge state distributions of proteins can be highly desirable in mass spectrometry experiments. In the present work, we implemented a vapor introduction technique to an Agilent Jet Stream ESI (Agilent Technologies, Santa Clara, CA, USA) source. An apparatus was designed to allow for the enrichment of the nitrogen sheath gas with basic vapors. An optical setup, using laser-induced fluorescence and a pH-chromic dye, permits the pH profiling of the droplets as they evaporate in the electrospray plume. Mechanisms of pH droplet modification and its effect on the protein charging phenomenon are elucidated. An important finding is that the enrichment with basic vapors of the nitrogen sheath gas, which surrounds the nebulizer spray, leads to an increase in the spray current. This is attributed to an increase in the electrical conductivity of water-amine enriched solvent at the tip exit. Here, the increased current results in a generation of additional electrolytically produced OH(-) ions and a corresponding increase in the pH at the tip exit. Along the electrospray plume, the pH of the droplets increases due to both droplet evaporation and exposure to basic vapors from the seeded sheath gas. The pH evolution in the ESI plume obtained using pure and basic seeded sheath gas was correlated with the evolution of the charge state distribution observed in mass spectra of proteins, in the negative ion mode. Taking advantage of the Agilent Jet Stream source geometry, similar protein charge state distributions and ion intensities obtained with basic initial solutions, can be obtained using native solution conditions by seeding the heated sheath gas with basic vapors. PMID:22565506

  19. Chemical analysis of raw and processed Fructus arctii by high-performance liquid chromatography/diode array detection-electrospray ionization-mass spectrometry

    PubMed Central

    Qin, Kunming; Liu, Qidi; Cai, Hao; Cao, Gang; Lu, Tulin; Shen, Baojia; Shu, Yachun; Cai, Baochang

    2014-01-01

    Background: In traditional Chinese medicine (TCM), raw and processed herbs are used to treat the different diseases. Fructus Arctii, the dried fruits of Arctium lappa l. (Compositae), is widely used in the TCM. Stir-frying is the most common processing method, which might modify the chemical compositions in Fructus Arctii. Materials and Methods: To test this hypothesis, we focused on analysis and identification of the main chemical constituents in raw and processed Fructus Arctii (PFA) by high-performance liquid chromatography/diode array detection-electrospray ionization-mass spectrometry. Results: The results indicated that there was less arctiin in stir-fried materials than in raw materials. however, there were higher levels of arctigenin in stir-fried materials than in raw materials. Conclusion: We suggest that arctiin reduced significantly following the thermal conversion of arctiin to arctigenin. In conclusion, this finding may shed some light on understanding the differences in the therapeutic values of raw versus PFA in TCM. PMID:25422559

  20. Reducing the negative effects of chemical polishing in acrylic resins by use of an additional cycle of polymerization

    Microsoft Academic Search

    José Antônio Nunes de Mello; Katia Olmedo Braun; Rodrigo Nunes Rached; Altair Antoninha Del Bel Cury

    2003-01-01

    Statement of problemThe chemical polishing of dentures and orthodontic appliances is an efficient and time-saving technique. However, the process may adversely affect the physical properties of resin.

  1. Ambient ionization mass spectrometry: a tutorial.

    PubMed

    Huang, Min-Zong; Cheng, Sy-Chi; Cho, Yi-Tzu; Shiea, Jentaie

    2011-09-19

    Ambient ionization is a set of mass spectrometric ionization techniques performed under ambient conditions that allows the direct analysis of sample surfaces with little or no sample pretreatment. Using combinations of different types of sample introduction systems and ionization methods, several novel techniques have been developed over the last few years with many applications (e.g., food safety screening; detection of pharmaceuticals and drug abuse; monitoring of environmental pollutants; detection of explosives for antiterrorism and forensics; characterization of biological compounds for proteomics and metabolomics; molecular imaging analysis; and monitoring chemical and biochemical reactions). Electrospray ionization and atmospheric pressure chemical ionization are the two main ionization principles most commonly used in ambient ionization mass spectrometry. This tutorial paper provides a review of the publications related to ambient ionization techniques. We describe and compare the underlying principles of operation, ionization processes, detecting mass ranges, sensitivity, and representative applications of these techniques. PMID:21819855

  2. Wafer Treatment Using Electrolysis-Ionized Water

    Microsoft Academic Search

    Hidemitsu Aoki; Masaharu Nakamori; Nahomi Aoto; Eiji Ikawa

    1994-01-01

    Electrolysis-ionized water treatment is shown to be useful for removing polystyrene particles from contact holes, silicon surface cleaning and the removal of metal contamination such as copper. Electrolysis-ionized waterhas a controllable pH and a higher oxidation-reduction potential than chemicals. Moreover, this water does notcontain acid or alkaline chemicals, and can easily be neutralized without adding chemicals. Electrolysis-ionized water treatment has

  3. Wafer Treatment Using Electrolysis-Ionized Water

    NASA Astrophysics Data System (ADS)

    Aoki, Hidemitsu; Nakamori, Masaharu; Aoto, Nahomi; Ikawa, Eiji

    1994-10-01

    Electrolysis-ionized water treatment is shown to be useful for removing polystyrene particles from contact holes, silicon surface cleaning and the removal of metal contamination such as copper. Electrolysis-ionized waterhas a controllable pH and a higher oxidation-reduction potential than chemicals. Moreover, this water does notcontain acid or alkaline chemicals, and can easily be neutralized without adding chemicals. Electrolysis-ionized water treatment has great potential for ecologically safe and low cost semiconductor processing.

  4. Dicarboxylic degradation products of nonylphenol polyethoxylates: synthesis and identification by gas chromatography-mass spectrometry using electron and chemical ionization modes.

    PubMed

    Hoai, Pham Manh; Tsunoi, Shinji; Ike, Michihiko; Inui, Naoko; Tanaka, Minoru; Fujita, Masanori

    2004-12-17

    The synthesis, mass spectra and detectability of four selected dicarboxylic degradation products (CAPECs) of nonylphenol polyethoxylates (NPEOs) are reported. The selected isomers have an alpha,alpha-dimethyl configuration (expressed as "dm" in their abbreviation), five to eight C atoms and a carboxyl group in the alkyl chain, and a carboxymethoxy acid group (dm-CA5-8P1ECs). The synthesis was successfully accomplished via a reaction sequence that started from anisole. After trimethylsilylation with N,O-bis(trimethylsilyl)acetamide or methylation with (trimethylsilyl)diazomethane, the derivatives of the dm-CA5-8P1ECs were subjected to a GC-electron ionization (EI)-MS and GC-isobutane chemical ionization (CI)-MS. In EI-MS, ion peaks at m/z = 265 and 207, corresponding to the alpha,alpha-dimethyl structures via the benzyl cleavage of carboxyalkyl chain, were the most significant ions of the trimethylsilyl and methyl derivatives, respectively. In CI-MS, the main ion peaks of dm-CA5-, dm-CA6-, dm-CA7-, and dm-CA8P1EC after methylation were at m/z= 129, 143, 157, and 171, respectively, corresponding to the loss of methyl phenoxyacetate from [M+ H]+; meanwhile significant peaks were detected at 321, 335, 349, and 363, corresponding to the loss of the trimethylsilanol after trimethylsilylation. The potential for the identification and quantification of individual branched carboxyalkyl isomeric mixtures of CA5-, CA6-, CA7-, and CA8P1EC metabolites based on corresponding dm-CA5-8P1ECs revealed the advantage of the GC-CI-MS although the detection limits in CI were clearly higher than those in EI. PMID:15633752

  5. Quantitative determination of endogenous sorbitol and fructose in human nerve tissues by atmospheric-pressure chemical ionization liquid chromatography/tandem mass spectrometry.

    PubMed

    Liang, H R; Takagaki, T; Foltz, R L; Bennett, P

    2005-01-01

    Attachment of anions to sorbitol and fructose has been shown to enhance sensitivity in both electrospray ionization (ESI) and atmospheric-pressure chemical ionization (APCI) mass spectrometry. The post-column addition of CHCl3 produced Cl-adducts of sorbitol and fructose but their signals were suppressed due to the elevated background. Different chlorinated compounds and different additive methods were systematically investigated to form more abundant Cl-adduct precursor ions and deprotonated product ions. The major causes of the high background were explored and effective methods were developed to improve the signal-to-noise ratios and reproducibility. The compositions of mobile phase, percentages of organic modifiers (MeCN, MeOH and water), columns, oven temperature, flow rates and different gradients were investigated to separate sorbitol from fructose along with their isomers including glucose, galactose, mannose, sorbose, mannitol, and dulcitol. The optimized separation was achieved on a Luna 5 mu NH2 100A column (150 x 4.6 mm) using a mobile phase containing MeCN with 0.1% of CH2Cl2 and 50% MeOH in water at a flow rate of 800 microL/min and an oven temperature of 40 degrees C using a gradient liquid chromatography (LC) system. Human nerve tissue samples were extracted by protein precipitation followed by mixed-mode solid-phase extraction. The LC/ESI-MS/MS method produced higher peak intensities than LC/APCI-MS/MS. However, there were matrix effects from extracted tissues in LC/ESI-MS/MS but not in LC/APCI-MS/MS. Consequently, APCI proved to be the more effective method of ionization. Then the LC/APCI-MS/MS method was fully validated and successfully applied to analysis of clinical samples. The concentrations of endogenous sorbitol and fructose were determined using calibration curves employing sorbitol-13C6 and fructose-13C6 as surrogate analytes. The method has provided excellent intra- and inter-assay precision and accuracy with linear ranges of 0.2-80 ng/mg for sorbitol and 1-400 ng/mg for fructose in human nerve tissues. PMID:16034846

  6. Implementation of Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry in Routine Clinical Laboratories Improves Identification of Coagulase-Negative Staphylococci and Reveals the Pathogenic Role of Staphylococcus lugdunensis.

    PubMed

    Argemi, Xavier; Riegel, Philippe; Lavigne, Thierry; Lefebvre, Nicolas; Grandpré, Nicolas; Hansmann, Yves; Jaulhac, Benoit; Prévost, Gilles; Schramm, Frédéric

    2015-07-01

    The use of matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) for staphylococcal identification is now considered routine in laboratories compared with the conventional phenotypical methods previously used. We verified its microbiological relevance for identifying the main species of coagulase-negative staphylococci (CoNS) by randomly selecting 50 isolates. From 1 January 2007 to 31 August 2008, 12,479 staphylococci were isolated with phenotypic methods, of which 4,594 were identified as Staphylococcus aureus and 7,885 were coagulase negative staphylococci. Using MALDI-TOF MS from 1 January 2011 to 31 August 2012, 14,913 staphylococci were identified, with 5,066 as S. aureus and 9,847 as CoNS. MALDI-TOF MS allowed the identification of approximately 85% of the CoNS strains, whereas only 14% of the CoNS strains were identified to the species level with phenotypic methods because they were often considered contaminants. Furthermore, the use of MALDI-TOF MS revealed the occurrence of recently characterized Staphylococcus species, such as S. pettenkoferi, S. condimenti, and S. piscifermentans. Microbiological relevance analysis further revealed that some species displayed a high rate of microbiological significance, i.e., 40% of the S. lugdunensis strains included in the analysis were associated with infection risk. This retrospective microbiological study confirms the role of MALDI-TOF MS in clinical settings for the identification of staphylococci with clinical consequences. The species distribution reveals the occurrence of the recently identified species S. pettenkoferi and putative virulent species, including S. lugdunensis. PMID:25878345

  7. Negative ion source

    DOEpatents

    Leung, K.N.; Ehlers, K.W.

    1984-12-04

    An ionization vessel is divided into an ionizing zone and an extraction zone by a magnetic filter. The magnetic filter prevents high-energy electrons from crossing from the ionizing zone to the extraction zone. A small positive voltage impressed on a plasma grid, located adjacent an extraction grid, positively biases the plasma in the extraction zone to thereby prevent positive ions from migrating from the ionizing zone to the extraction zone. Low-energy electrons, which would ordinarily be dragged by the positive ions into the extraction zone, are thereby prevented from being present in the extraction zone and being extracted along with negative ions by the extraction grid. Additional electrons are suppressed from the output flux using ExB drift provided by permanent magnets and the extractor grid electrical field. 14 figs.

  8. Negative ion source

    DOEpatents

    Leung, Ka-Ngo (Hercules, CA); Ehlers, Kenneth W. (Alamo, CA)

    1984-01-01

    An ionization vessel is divided into an ionizing zone and an extraction zone by a magnetic filter. The magnetic filter prevents high-energy electrons from crossing from the ionizing zone to the extraction zone. A small positive voltage impressed on a plasma grid, located adjacent an extraction grid, positively biases the plasma in the extraction zone to thereby prevent positive ions from migrating from the ionizing zone to the extraction zone. Low-energy electrons, which would ordinarily be dragged by the positive ions into the extraction zone, are thereby prevented from being present in the extraction zone and being extracted along with negative ions by the extraction grid. Additional electrons are suppressed from the output flux using ExB drift provided by permanent magnets and the extractor grid electrical field.

  9. Microprobe sampling--photo ionization-time-of-flight mass spectrometry for in situ chemical analysis of pyrolysis and combustion gases: examination of the thermo-chemical processes within a burning cigarette.

    PubMed

    Hertz, Romy; Streibel, Thorsten; Liu, Chuan; McAdam, Kevin; Zimmermann, Ralf

    2012-02-10

    A microprobe sampling device (?-probe) has been developed for in situ on-line photo ionization mass spectrometric analysis of volatile chemical species formed within objects consisting of organic matter during thermal processing. With this approach the chemical signature occurring during heating, pyrolysis, combustion, roasting and charring of organic material within burning objects such as burning fuel particles (e.g., biomass or coal pieces), lit cigarettes or thermally processed food products (e.g., roasting of coffee beans) can be investigated. Due to its dynamic changes between combustion and pyrolysis phases the cigarette smoking process is particularly interesting and has been chosen as first application. For this investigation the tip of the ?-probe is inserted directly into the tobacco rod and volatile organic compounds from inside the burning cigarette are extracted and real-time analyzed as the glowing front (or coal) approaches and passes the ?-probe sampling position. The combination of micro-sampling with photo ionization time-of-flight mass spectrometry (PI-TOFMS) allows on-line intrapuff-resolved analysis of species formation inside a burning cigarette. Monitoring volatile smoke compounds during cigarette puffing and smoldering cycles in this way provides unparalleled insights into formation mechanisms and their time-dependent change. Using this technique the changes from pyrolysis conditions to combustion conditions inside the coal of a cigarette could be observed directly. A comparative analysis of species formation within a burning Kentucky 2R4F reference cigarette with ?-probe analysis reveals different patterns and behaviors for nicotine, and a range of semi-volatile aromatic and aliphatic species. PMID:22244143

  10. Quantitation of triacylglycerols in edible oils by off-line comprehensive two-dimensional liquid chromatography-atmospheric pressure chemical ionization mass spectrometry using a single column.

    PubMed

    Wei, Fang; Hu, Na; Lv, Xin; Dong, Xu-Yan; Chen, Hong

    2015-07-24

    In this investigation, off-line comprehensive two-dimensional liquid chromatography-atmospheric pressure chemical ionization mass spectrometry using a single column has been applied for the identification and quantification of triacylglycerols in edible oils. A novel mixed-mode phenyl-hexyl chromatographic column was employed in this off-line two-dimensional separation system. The phenyl-hexyl column combined the features of traditional C18 and silver-ion columns, which could provide hydrophobic interactions with triacylglycerols under acetonitrile conditions and can offer ?-? interactions with triacylglycerols under methanol conditions. When compared with traditional off-line comprehensive two-dimensional liquid chromatography employing two different chromatographic columns (C18 and silver-ion column) and using elution solvents comprised of two phases (reversed-phase/normal-phase) for triacylglycerols separation, the novel off-line comprehensive two-dimensional liquid chromatography using a single column can be achieved by simply altering the mobile phase between acetonitrile and methanol, which exhibited a much higher selectivity for the separation of triacylglycerols with great efficiency and rapid speed. In addition, an approach based on the use of response factor with atmospheric pressure chemical ionization mass spectrometry has been developed for triacylglycerols quantification. Due to the differences between saturated and unsaturated acyl chains, the use of response factors significantly improves the quantitation of triacylglycerols. This two-dimensional liquid chromatography-mass spectrometry system was successfully applied for the profiling of triacylglycerols in soybean oils, peanut oils and lord oils. A total of 68 triacylglycerols including 40 triacylglycerols in soybean oils, 50 triacylglycerols in peanut oils and 44 triacylglycerols in lord oils have been identified and quantified. The liquid chromatography-mass spectrometry data were analyzed using principal component analysis. The results of the principal component analysis enabled a clear identification of different plant oils. By using this two-dimensional liquid chromatography-mass spectrometry system coupled with principal component analysis, adulterated soybean oils with 5% added lord oil and peanut oils with 5% added soybean oil can be clearly identified. PMID:26070817

  11. Part-per-trillion level determination of antifouling pesticides and their byproducts in seawater samples by off-line solid-phase extraction followed by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Martínez, K; Ferrer, I; Barceló, D

    2000-05-19

    A new method for the simultaneous determination of antifouling pesticides and some of their byproducts such as dichlofluanid, diuron and its byproducts [demethyldiuron and 1-(3,4-dichlorophenyl)urea], (2-thiocyanomethylthio)ben: zothiazole, chlorothalonil, Sea-nine 211, Irgarol 1051 and one of its byproducts (2-methylthio-4-tert.-butylamino-s-triazine) in seawater was developed. The extraction of these compounds from the filtered seawater samples was performed off-line with different solid-phase extraction sorbents using (I) a 500 mg graphitized carbon black cartridge (ENVI-Carb) and (II) 200 mg polymeric cartridges (LiChrolut EN and Isolute ENV+) and passing 500 ml of the sample through these cartridges. The detection was carried out by reversed-phase high-performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry both in the negative and positive ion modes. The recovery ranged from 76 to 96% for the whole antifouling group with the ENVI-Carb cartridges and the detection limit was at the part-per-trillion level except for TCMTB. The method utilizing the polymeric cartridge proved to be very useful, time saving and with good recoveries when only Irgarol and its byproduct, Sea-nine 211 and diuron and its byproducts, have to be analyzed. The different cartridges were applied to the analysis of these pesticides in different marinas of the Catalan coast; diuron, dichlofluanid, Sea-nine 211, Irgarol as well as demethyldiuron and the Irgarol byproduct being the must ubiquitous pollutants. Maximum concentration levels were 2-3.5 microg/l of diuron and Sea-nine 211, respectively. PMID:10870693

  12. N2O5 measurement in Hong Kong by a chemical ionization mass spectrometry: Presence of high N2O5 and implications

    NASA Astrophysics Data System (ADS)

    Jun, Tham Yee; Tao, Wang; Zhe, Wang; Xinfeng, Wang; Chao, Yan; Qiaozhi, Zha; Zheng, Xu; Likun, Xue

    2014-05-01

    Dinitrogen pentoxide (N2O5) plays key roles in a number of nocturnal chemical processes within the troposphere, including the sink of nitrogen oxides (NOx). However, accurate measurement of this atmospheric trace compound remains as a challenging task, especially in polluted environment like China. We initially deploy a thermal dissociation chemical ionization mass spectrometry (TD-CIMS) for N2O5 field measurement in Hong Kong from 2010-2012. Unusual high N2O5 signal measured as NO3- (62 amu) were frequently observed. Various interference tests and correction were conducted to verify the data, but we caution the use of 62 amu for measuring ambient N2O5 in a high NOx environment like Hong Kong. Therefore, we optimized the CIMS to measure N2O5 as ion cluster of I(N2O5)- at 235 amu with some minor improvements and demonstrated to has the ability for simultaneous in situ measurements of N2O5 at an urban site. Then, the CIMS was deployed to another field study at a mountain-top site (Tai Mo Shan). A comparison of N2O5 measurement with a cavity ring-down spectrometry was performed and found to be in good correlation with the CIMS. High concentration of N2O5 was observed between the boundary layer and there are some occasions where N2O5 exceeds several ppb, which is among the highest values ever reported. These results provide deeper understanding on the chemistry of NOx in a polluted environment. Furthermore, our first observation of nitryl chloride (ClNO2) and its co-existence with N2O5 also implies an active heterogeneous reactivity between N2O5 and chloride particles in an Asian environment. Thus, N2O5 is an important nocturnal intermediate and has the potential in jump-starting the atmospheric photochemistry in this region

  13. The role of physical and chemical properties of Pd nanostructured materials immobilized on inorganic carriers on ion formation in atmospheric pressure laser desorption/ionization mass spectrometry.

    PubMed

    Silina, Yuliya E; Koch, Marcus; Volmer, Dietrich A

    2014-06-01

    Fundamental parameters influencing the ion-producing efficiency of palladium nanostructures (nanoparticles [Pd-NP], nanoflowers, nanofilms) during laser irradiation were studied in this paper. The nanostructures were immobilized on the surface of different solid inorganic carrier materials (porous and mono-crystalline silicon, anodic porous aluminum oxide, glass and polished steel) by using classical galvanic deposition, electroless local deposition and sputtering. It was the goal of this study to investigate the influence of both the nanoparticular layer as well as the carrier material on ion production for selected analyte molecules. Our experiments demonstrated that the dimensions of the synthesized nanostructures, the thickness of the active layers, surface disorders, thermal conductivity and physically or chemically adsorbed water influenced signal intensities of analyte ions during surface-assisted laser desorption/ionization (SALDI) while no effects such as plasmon resonance, photoelectric effect or catalytic activity were expected to occur. Excellent LDI abilities were seen for Pd-NPs immobilized on steel, while Pd nanoflowers on porous silicon exhibited several disadvantages; viz, strong memory effects, dependency of the analytical signal on amount of physically and chemically adsorbed water inside porous carrier, reduced SALDI activity from unstable connections between Pd and semiconductor material, decrease of the melting point of pure silicon after Pd immobilization and resulting strong laser ablation of metal/semiconductor complex, as well as significantly changed surface morphology after laser irradiation. The analytical performance of Pd-NP/steel was further improved by applying a hydrophobic coating to the steel surface before galvanic deposition. This procedure increased the distance between Pd-NPs, thus reducing thermal stress upon LDI; it simultaneously decreased spot sizes of deposited sample solutions. PMID:24913399

  14. Flavor release measurement by atmospheric pressure chemical ionization ion trap mass spectrometry, construction of interface and mathematical modeling of release profiles.

    PubMed

    Haahr, Anne-Mette; Madsen, Henrik; Smedsgaard, Jørn; Bredie, Wender L P; Stahnke, Louise H; Refsgaard, Hanne H F

    2003-02-01

    An instrumental on-line retronasal flavor analysis was developed to obtain information about the release of flavor compounds in expired air from humans during eating. The volatile flavor compounds were measured by ion trap mass spectrometry with an atmospheric pressure chemical ionization source (APCI). An interface was designed to sample the breath directly from the nose. The repeatability in vitro for seven different flavor compounds came out with relative standard derivation less than 10% in most cases, which is acceptable. In vitro quantification was carried out by a determination of the concentration in the gas phase over a flavor solution by GC/MS, followed by measurements of intensities by the APCI ion trap. Ion suppression by acetone in the breath was negligible at concentration levels relevant in these experiments. The instrumental limits of detection for menthone and menthol coincide with that of the flavor detection threshold. An application study on the release of menthone and menthol from chewing gum by a group of six test persons was performed. Flavored chewing gum was used as a model matrix because of the long chewing periods and the simplicity of the system. It is concluded that the interface and the method can be used to measure breath from the nose. A mathematical model of the data was developed to give a quantitative method for description and characterization of the release of flavor compounds. The release profiles consisted of two sequences, one for a chewing period, and one for a phasing out process. The proposed method for modeling provided a reasonable description of the release process. In addition to flavor compounds, this new interface and mathematical application could provide information on chemicals in the human breath, which could be interesting, for example, within medical diagnosis. PMID:12585498

  15. Characterization of cis-9 trans-11 trans-15 C18:3 in milk fat by GC and covalent adduct chemical ionization tandem MS

    PubMed Central

    Gómez-Cortés, Pilar; Tyburczy, Cynthia; Brenna, J. Thomas; Juárez, Manuela; de la Fuente, Miguel Angel

    2009-01-01

    Rumen biohydrogenation of dietary ?-linolenic acid gives rise in ruminants to accumulation of fatty acid intermediates, some of which may be transferred into milk. Rumelenic acid [cis-9 trans-11 cis-15 C18:3 (RLnA)] has recently been characterized, but other C18:3 minor isomers are still unknown. The objective of this work was to identify a new isomer of octatridecenoic acid present in milk fat from ewes fed different sources of ?-linolenic acid. Structural characterization of this fatty acid was achieved by GC-MS. Analysis of dimethyloxazoline and picolinyl ester derivatives allowed for location of the double bond positions. Covalent adduct chemical ionization tandem mass spectrometry confirmed the positional structure 9-11-15, identical to RLnA, and helped to establish double bond geometry (cis-trans-trans). This new C18:3 isomer could be formed by isomerization of cis-15 bond of RLnA and subsequently converted by hydrogenation to trans-11 trans-15 C18:2, an octadecadienoic acid also detected in this study. PMID:19542528

  16. Studies of the role of metastables and doubly ionized species in the chemical and thermal structure of the Venusian and Martian ionospheres

    NASA Technical Reports Server (NTRS)

    Fox, J. L.

    1981-01-01

    Models of the upper atmospheres of Mars and Venus were constructed using Viking and Pioneer Venus data. The neutral densities, with the exception of NO, N(4S), N(2D) and N(2P) were taken from the measured values, along with the neutral, ion, and electron temperatures. Using solar fluxes and relevant cross sections, the production rates of ions and neutral fragments by photo and electron impact processes were computed. These production rates were combined with chemical production rates and loss along with one dimensional transport eddy diffusion, molecular and ambi polar diffusion, and thermal diffusion, to determine the densities of ions and odd nitrogen species. Preliminary calculations show that the chemistry of metastables and doubly ionized species is important in the ionospheres of Mars and Venus. Production of N(+) in metastable reactions is particularly important, and it explains the discrepancy between the measurements of earlier models. Production of CO(+) is also affected. Reactions of O(++) and O(+)(2D) with N2 have important consequences for the escape rate of atomic nitrogen from the Martian atmosphere.

  17. Trace analysis of selected hormones and sterols in river sediments by liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Mati?, Ivana; Gruji?, Svetlana; Jaukovi?, Zorica; Lauševi?, Mila

    2014-10-17

    In this paper, development and optimization of new LC-MS method for determination of twenty selected hormones, human/animal and plant sterols in river sediments were described. Sediment samples were prepared using ultrasonic extraction and clean up with silica gel/anhydrous sodium sulphate cartridge. Extracts were analyzed by liquid chromatography-linear ion trap-tandem mass spectrometry, with atmospheric pressure chemical ionization. The optimized extraction parameters were extraction solvent (methanol), weight of the sediment (2 g) and time of ultrasonic extraction (3× 10 min). Successful chromatographic separation of hormones (estriol and estrone, 17?- and 17?-estradiol) and four human/animal sterols (epicoprostanol, coprostanol, ?-cholestanol and ?-cholestanol) that have identical fragmentation reactions was achieved. The developed and optimized method provided high recoveries (73-118%), low limits of detection (0.8-18 ng g(-1)) and quantification (2.5-60 ng g(-1)) with the RSDs generally lower than 20%. Applicability of the developed method was confirmed by analysis of six river sediment samples. A widespread occurrence of human/animal and plant sterols was found. The only detected hormone was mestranol in just one sediment sample. PMID:25182857

  18. Identification and quantification of antitumor thioproline and methylthioproline in Korean traditional foods by a liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Kim, Sun Hyo; Kim, Hyun-Ji; Shin, Ho-Sang

    2014-11-01

    A liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometric method (LC-APCI-MS/MS) has been developed for the sensitive determination of antitumor thioproline and methylthioproline from fermented foods. Thioproline and methylthioproline were derivatized in one step with ethyl chloroformate at room temperature. These compounds were identified and quantified in various traditional Korean fermented foods by LC-APCI-MS/MS. The concentration range of thioproline of each food was found for doenjang (0.011-0.032mg/kg), gochujang (0.010-0.038mg/kg), and ganjang (0.010-0.038mg/kg). Those of methylthioproline of each food was found for doenjang (0.098-0.632mg/kg), gochujang (0.015-0.112mg/kg), and ganjang (0.023-1.468mg/kg). A prolonged aging time leads to an increase in both the thioproline and methylthioproline contents, suggesting that the storage time plays a key role in the formation of thioproline and methylthioproline in Korean traditional foods. The results here suggest that thioproline and methylthioproline are related to the biological activities of traditional Korean fermented foods. PMID:25128876

  19. Phenyl-modified reversed-phase liquid chromatography coupled to atmospheric pressure chemical ionization mass spectrometry: a universal method for the analysis of partially oxidized aromatic hydrocarbons.

    PubMed

    Letzel, T; Pöschl, U; Wissiack, R; Rosenberg, E; Grasserbauer, M; Niessner, R

    2001-04-01

    A new liquid chromatographic method for the efficient separation of aromatic compounds having a wide range of sizes, molecular structures, and polarities has been developed. Based on a phenyl-modified silica reversed stationary phase and a methanol-water solvent gradient, it allows the separation of mono- and polycyclic aromatic hydrocarbons (PAHs) having up to five condensed aromatic rings and partially oxidized derivatives within a single chromatographic run of 40-min duration. The applicability of the method is demonstrated using 81 reference substances (PAHs, phenols, quinones, acids, lactones, esters, etc.) and real samples of environmental, medical, and technical relevance (ozonized PAHs, lake water, human urine, diesel exhaust condensates). The retention times of the investigated aromatics exhibit a regular increase with molecular mass and a systematic decrease with increasing number and polarity of functional groups. In case of intramolecular hydrogen bonding, a positive shift of retention time provides additional structural information. The combination of chromatographic retention time with the molecular mass and structural information from mass spectrometric detection allows the tentative identification of unknown aromatic analytes at trace levels, even without specific reference substances. With atmospheric pressure chemical ionization (APCI), low detection limits and highly informative fragmentation patterns can be obtained by in-source collision-induced fragmentation in a single-quadrupole LC-APCI-MS system as applied in this study, and multidimensional MS experiments are expected to further enhance the potential of the presented method. PMID:11321321

  20. Localization of double bonds in triacylglycerols using high-performance liquid chromatography/atmospheric pressure chemical ionization ion-trap mass spectrometry.

    PubMed

    Háková, Eva; Vrkoslav, Vladimír; Míková, Radka; Schwarzová-Pecková, Karolina; Bosáková, Zuzana; Cva?ka, Josef

    2015-07-01

    A method for localizing double bonds in triacylglycerols using high-performance liquid chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization (APCI) was developed. The technique was based on collision-induced dissociation or pulsed Q collision-induced dissociation of the C3H5N(+•) adducts ([M + 55](+•)) formed in the presence of acetonitrile in the APCI source. The spectra were investigated using a large series of standards obtained from commercial sources and prepared by randomization. The fragmentation spectra made it possible to determine (i) the total number of carbons and double bonds in the molecule, (ii) the number of carbons and double bonds in acyls, (iii) the acyl in the sn-2 position on the glycerol backbone, and (iv) the double-bond positions in acyls. The double-bond positions were determined based on two types of fragments (alpha and omega ions) formed by cleavages of C-C bonds vinylic to the original double bond. The composition of the acyls and their positions on glycerol were established from the masses and intensities of the ions formed by the elimination of fatty acids from the [M + 55](+•) precursor. The method was applied for the analysis of triacylglycerols in olive oil and vernix caseosa. Graphical Abstract The diagnostic fragments in the APCI PQD MS(2) spectrum of the [M + 55](+•) adduct of triolein. PMID:25701424

  1. Interaction of the indoor air pollutant acetone with Degussa P25 TiO2 studied by chemical ionization mass spectrometry.

    PubMed

    Schmidt, Catherine M; Weitz, Eric; Geiger, Franz M

    2006-11-01

    Preventing a build-up of indoor pollutant concentrations has emerged as a major goal in environmental chemistry. Here, we have applied chemical ionization mass spectrometry to study the interaction of acetone, a common indoor air pollutant, with Degussa P25 TiO2, an inexpensive catalyst that is widely used for the degradation of volatile organic compounds into CO2 and water. To better understand the adsorption of acetone onto Degussa P25, the necessary first step for its degradation, the experiments were carried out at room temperature in the absence of UV light. This allowed for the deconvolution of the nonreactive and reactive thermal binding processes on Degussa P25 at acetone partial pressures (10(-7)-10(-4) Torr) commonly found in indoor environments. On average, 30% of the adsorbed acetone is bound irreversibly, resulting in a surface coverage of irreversibly bound acetone of approximately 1 x 10(12) molecules/cm2 at 3-4 x 10(-5) Torr. Equilibrium and dynamic experiments yield a sticking coefficient of approximately 1 x 10(-4) that is independent of the acetone partial pressures examined here. Equilibrium binding constants and free energies of adsorption are reported. PMID:17073491

  2. Molecular Characterization of S- and N-containing Organic Constituents in Ambient Aerosols by negative ion mode High-Resolution Nanospray Desorption Electrospray Ionization Mass Spectrometry: CalNex 2010 field study

    SciTech Connect

    O'Brien, Rachel E.; Laskin, Alexander; Laskin, Julia; Rubitschun, Caitlin L.; Surratt, Jason D.; Goldstein, Allen H.

    2014-11-27

    Samples of ambient aerosols from the 2010 California Research at the Nexus of Air Quality and Climate Change (CalNex) field study were analyzed using Nanospray Desorption Electrospray Ionization High Resolution Mass Spectrometry (nano-DESI/MS). Four samples per day were collected in Bakersfield, CA on June 20-24 with a collection time of 6 hours per sample. Four characteristic groups of organic constituents were identified in the samples: compounds containing carbon, hydrogen, and oxygen only (CHO), sulfur- (CHOS), nitrogen-(CHON), and both nitrogen- and sulfur-containing organics (CHONS). Within the groups, organonitrates, organosulfates, and nitroxy organosulfates were assigned based on accurate mass measurements and elemental ratio comparisons. Changes in the chemical composition of the aerosol samples were observed throughout the day. The number of observed CHO compounds increased in the afternoon samples, suggesting regional photochemical processing as a source. The average number of CHOS compounds had the smallest changes throughout the day, consistent with a more broadly distributed source. Both of the nitrogen-containing groups (CHON and CHONS) had greater numbers of compounds in the night and morning samples, indicating that nitrate radical chemistry was likely a source for those compounds. Most of the compounds were found in submicron particles. The size distribution of CHON compounds was bimodal. We conclude that the majority of the compounds observed were secondary in nature with both biogenic and anthropogenic sources.

  3. Determination of toluenediamine isomers by capillary gas chromatography and chemical ionization mass spectrometry with special reference to the biological monitoring of 2,4- and 2,6-toluene diisocyanate.

    PubMed

    Skarping, G; Dalene, M; Lind, P

    1994-03-11

    The determination of 2,3-, 3,4-, 2,6-, 2,4- and 2,5-toluenediamine (TDA) in hydrolysed human urine and blood plasma was studied by GC-MS. The TDA isomers as their perfluoro-fatty acid anhydride derivatives were investigated. Chemical ionization with ammonia and isobutane as reagent gas and monitoring both positive and negative ions are studied. Negative ion monitoring using ammonia and the TDA pentafluoropropionic anhydride (PFPA) derivatives were chosen owing to the low detection limits and good separations of the isomers studied. The ions monitored were m/z 394 and 374 corresponding to the (M-20)- and (M-40)- ions and the m/z = 397 and 377 ions of the tri-deuterium-labelled TDA used as an internal standard. The performance of 2,4-, 2,5- and 2,6-TDA-PFPA in the ion source was studied by varying the ammonia pressure, temperature and electron energy. A 1-ml volume of human urine was added to 1.5 ml of 6 M HCl containing 0.5 micrograms/l of each of the trideuterated 2,6- and 2,4-TDA and the solution was hydrolysed at 100 degrees C overnight. TDA was extracted into 2 ml of toluene by the addition of 5 ml of saturated NaOH solution. Derivatization was performed in toluene by the addition of 10 microliters of PFPA. The excesses of the reagent and acid formed were removed by extraction with 1 M phosphate buffer solution (pH 7.5). Analyses of 2,6-, 2,4- and 2,5-TDA-spiked human urine (0.2-2.5 micrograms/l) were performed. The correlation coefficients were 0.999 (n = 6). The precision (R.S.D.) for human urine spiked at 1 micrograms/l was 1.6% for 2.6-TDA, 3,5% for 2,4-TDA and 3.2% for 2,5-TDA (n = 10). The detection limit, defined as twice the signal-to-noise ratio, was 1-5 fg injected, corresponding to less than 0.05 micrograms/l of TDA in human urine or plasma. PMID:8173666

  4. Gridded electron reversal ionizer

    NASA Technical Reports Server (NTRS)

    Chutjian, Ara (Inventor)

    1993-01-01

    A gridded electron reversal ionizer forms a three dimensional cloud of zero or near-zero energy electrons in a cavity within a filament structure surrounding a central electrode having holes through which the sample gas, at reduced pressure, enters an elongated reversal volume. The resultant negative ion stream is applied to a mass analyzer. The reduced electron and ion space-charge limitations of this configuration enhances detection sensitivity for material to be detected by electron attachment, such as narcotic and explosive vapors. Positive ions may be generated by generating electrons having a higher energy, sufficient to ionize the target gas and pulsing the grid negative to stop the electron flow and pulsing the extraction aperture positive to draw out the positive ions.

  5. APPLICATION OF NEGATIVE ION CHEMICAL IONIZATION MASS SPECTROMETRY FOR THE ANALYSIS OF TRICHLOROPYRIDINOL IN SALIVA OF RATS EXPOSED TO CHLORPYRIFOS. (R828608)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  6. Differentiation of Positional Isomers of Hybrid Peptides Containing Repeats of ?-Nucleoside Derived Amino Acid (?-Nda-) and L-Amino Acids by Positive and Negative Ion Electrospray Ionization Tandem Mass Spectrometry (ESI-MS n )

    NASA Astrophysics Data System (ADS)

    Raju, B.; Ramesh, M.; Srinivas, R.; Chandrasekhar, S.; Kiranmai, N.; Sarma, V. U. M.

    2011-04-01

    A new class of positional isomeric pairs of -Boc protected oligopeptides comprised of alternating nucleoside derived ?-amino acid (?-Nda-) and L-amino acid residues (alanine, valine, and phenylalanine) have been differentiated by both positive and negative ion electrospray ionization ion-trap tandem mass spectrometry (ESI-MS n ). The protonated dipeptide positional isomers with ?-Nda- at the N-terminus lose CH3OH, NH3, and C2H4O2, whereas these processes are absent for the peptides with L-amino acids at the N-terminus. Instead, the presence of L-amino acids at the N-terminus results in characteristic retro-Mannich reaction involving elimination of imine. A good correlation has been observed between the conformational structure of the peptides and the abundance of y{n/+} and b{n/+} ions in MS n spectra. In the case of tetrapeptide isomers that are reported to form helical structures in solution phase, no y{n/+} and b{n/+} ions are observed when the corresponding amide -NH- participates in the helical structures. In contrast, significant y{n/+} and b{n/+} ions are formed when the amide -NH- is not involved in the H-bonding. In the case of tetra- and hexapeptides, it is observed that abundant b{n/+} ions are formed, presumably with stable oxazolone structures when the C-terminus of the b{n/+} ions possessed L-amino acid and the ?-Nda- at the C-terminus appears to prevent the cyclization process leading to the absence of corresponding b{n/+} ions.

  7. Sensitivity improvement in hydrophilic interaction chromatography negative mode electrospray ionization mass spectrometry using 2-(2-methoxyethoxy)ethanol as a post-column modifier for non-targeted metabolomics.

    PubMed

    Koch, Wendelin; Forcisi, Sara; Lehmann, Rainer; Schmitt-Kopplin, Philippe

    2014-09-26

    The application of ammonia acetate buffered liquid chromatography (LC) eluents is known to concomitantly lead to ion suppression when electrospray ionization mass spectrometry (ESI-MS) detection is used. In negative ESI mode, post column infusion of 2-(2-methoxyethoxy)ethanol (2-MEE) was shown in the literature to help to compensate this adverse effect occurring in reversed phase liquid chromatography mass spectrometry (RP-LC-MS) analyses. Here a setup of direct infusion and hydrophilic interaction chromatography (HILIC) post-column infusion experiments was established in order to investigate systematically the beneficial effects of 2-MEE. We demonstrate that, 2-MEE can help to improve ESI-MS sensitivity in HILIC too and reveal analyte structure specific behaviors. Our study indicates that 2-MEE especially improves ESI response for small and polar molecules. The ESI response of stable isotope labeled amino acids spiked into biological matrices increases up to 50-fold (i.e. D5-l-glutamic acid) when post column infusion of 2-MEE is applied. A non-targeted analysis of a pooled urine sample via HILIC-ESI-QTOF-MS supports this hypothesis. In direct infusion, the combined application of an ammonia acetate buffered solution together with 2-MEE results in an improved ESI response compared to a non-buffered solution. We observed up to 60-fold increased ESI response of l-lysine. We propose this effect is putatively caused by the formation of smaller ESI droplets and stripping of positive charge from ESI droplets due to evaporation of acetic acid anions. In summary, post-column infusion of 2-MEE especially enhances ESI response of small and polar molecules. Therefore it can be regarded as a valuable add-on in targeted or non-targeted metabolomic HILIC-MS studies since this method sets a focus on this molecule category. PMID:25160955

  8. A Chemical Ionization High-Resolution Time-of-Flight Mass Spectrometer Coupled to a Micro Orifice Volatilization Impactor (MOVI-HRToF-CIMS) for Analysis of Gas and Particle-Phase Organic Species

    Microsoft Academic Search

    Reddy L. N. Yatavelli; Felipe Lopez-Hilfiker; Julia D. Wargo; Joel R. Kimmel; Michael J. Cubison; Timothy H. Bertram; Jose L. Jimenez; Marc Gonin; Douglas R. Worsnop; Joel A. Thornton

    2012-01-01

    We describe a new instrument, chemical ionization high-resolution time-of-flight mass spectrometer coupled to a micro-orifice volatilization impactor (MOVI-HRToF-CIMS). The MOVI-HRToF-CIMS instrument is unique in that, within a compact field-deployable package, it provides (1) quantifiable molecular-level information for both gas and particle phase organic species on timescales ranging from ?1 second for gases and 10 - 60 minutes for particle-phase compounds

  9. High-Throughput Walkthrough Detection Portal as a Measure for Counter Terrorism: Design of a Vapor Sampler for Detecting Triacetone Triperoxide Vapor by Atmospheric-Pressure Chemical-Ionization Ion-Trap Mass Spectrometry

    Microsoft Academic Search

    Yasuaki Takada; Yasutaka Suzuki; Hisashi Nagano; Masuyuki Sugiyama; Eri Nakajima; Masakazu Sugaya; Yuichiro Hashimoto; Minoru Sakairi

    2012-01-01

    Aiming to prevent terrorist attacks in places where many people are coming and going, we have been developing a “high-throughput detection portal system.” The portal system consists of a vapor sampler, an atmospheric-pressure chemical-ionization ion source, and an explosives detector based on ion-trap mass spectrometry. The vapor sampler was designed to be installed in an automated ticket gate of a

  10. Screening for library-assisted identification and fully validated quantification of 22 beta-blockers in blood plasma by liquid chromatography–mass spectrometry with atmospheric pressure chemical ionization

    Microsoft Academic Search

    Hans H. Maurer; Oliver Tenberken; Carsten Kratzsch; Armin A. Weber; Frank T. Peters

    2004-01-01

    A liquid chromatographic–mass spectrometric assay with atmospheric pressure chemical ionization (LC–APCI–MS) is presented for screening for, library-assisted identification (both in scan mode) and quantification (selected-ion mode) of the beta-blockers acebutolol, diacetolol, alprenolol, atenolol, betaxolol, bisoprolol, bupranolol, carazolol, carteolol, carvedilol, celiprolol, esmolol, labetalol, metoprolol, nadolol, nebivolol, oxprenolol, penbutolol, propranolol, sotalol, talinolol and timolol in blood plasma after mixed-mode (HCX) solid-phase extraction

  11. On-line acquisition, analysis, and e-mailing of high-resolution exact-mass electron impact\\/chemical ionization mass spectrometry data acquired using an automated direct probe

    Microsoft Academic Search

    Nelson Huang; Marshall M. Siegel; Helmut Muenster; Klaus Weissenberg

    1999-01-01

    A complete automation package has been developed for data acquisition, processing, interpreting, and e-mailing of high-resolution\\u000a exact-mass electron impact (EI) and chemical ionization (CI) mass spectrometry data. A commercial high performance magnetic\\u000a sector mass spectrometer equipped with a commercial programmable robotic direct probe was used. The software package contains\\u000a a series of modules that automatically performs all the functions necessary

  12. Negative ions

    Microsoft Academic Search

    H. Massey

    1976-01-01

    Topics covered include: the negative ion of hydrogen; ground states of complex atomic negative ions-theoretical considerations; the electron affinities of the elements; atomic negative ions-excited states-autodetachment, general account; autodetaching states of specific atomic negative ions; molecular negative ions-ground states; excited electronic states of molecular negative ions; modes of formation of negative ions-formation by radiative processes-radiative attachment and polar photodissociation; modes

  13. Determination of 2-phenylethylamine in rat brain after MAO inhibitors, and in human CSF and urine by capillary GC and chemical ionization MS.

    PubMed

    Lauber, J; Waldmeier, P C

    1984-01-01

    A highly specific and sensitive method for the determination of beta-phenylethylamine (PEA) in biological material is presented. It involves prepurification of the extracts on Sep-Pak C18 cartridges, derivatization with heptafluorobutyric acid anhydride, gas chromatography on 50 m capillary columns and quantification by chemical ionization mass spectrometry. Using this method, levels of PEA in the rat brain and the effects of various monoamine oxidase (MAO) inhibitors thereon have been determined. PEA control levels were found to vary considerably: the lowest and highest values found were 0.4 and 12.5 ng/g tissue (n = 25). Within one and the same control group, the variation was somewhat smaller. The preferential or specific inhibitors of MAO A, amiflamine, cimoxatone, CGP 11305 A, moclobemide and toloxatone did not alter rat brain PEA even at high doses. In contrast, the preferential inhibitors of MAO B, deprenil, pargyline and MD 780236, as well as the nonselective agent tranylcypromine, caused strong (up to about 60-fold) increases. The threshold doses corresponded to those which caused about an 80% inhibition of MAO B as measured ex vivo. The method was also used to determine the concentration of PEA in human CSF (mean 17.3 +/- 3.3 ng/ml, range 3-45 ng/ml, n = 15) and urine (males: mean 35 +/- 5 micrograms/g creatinine, range 3.8 - 219 micrograms/g, 78 control days of a total of 12 subjects; females: mean 35 +/- 6 micrograms/g creat., range 2.7 - 266 micrograms/g, 55 control days of a total of 8 subjects). PMID:6527139

  14. Qualitative and quantitative analysis on chemical constituents from Curculigo orchioides using ultra high performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    He, Yongjing; Dong, Xin; Jia, Xiaoxuan; Li, Mei; Yuan, Tingting; Xu, Hongtao; Qin, Luping; Han, Ting; Zhang, Qiaoyan

    2015-01-01

    A rapid ultra-high performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UHPLC-ESI-Q-TOF/MS) method was developed for qualitative and quantitative determination of constituents in the rhizome of Curculigo orchioides. Qualitative analysis was performed on a Waters ACQUITY UHPLC @ HSS T3 column (1.8 ?m 100 × 2.1mm) using gradient elution with mobile phase of 0.1% formic acid and acetonitrile. Quantitative analysis was performed on an Agilent ZORBAX Eclipse plus C18 column (1.7 ?m 100 × 2.1mm) using gradient elution with mobile phase of 0.1% acetic acid and acetonitrile for at least 20 min. Quadrupole TOF/MS in either full scan mode or extracted ion mode was used for qualitative and quantitative analysis of the constituents. According to the mass spectrometric fragmentation mechanism and UHPLC-ESI-Q-TOF-MS data, chemical structures of 45 constituents in the rhizome of Curculigo orchioides, including 19 phenols and phenolic glycosides, 16 lignans and lignan glycosides, 8 triterpenoid saponins, one flavone and one sesquiterpene, were identified tentatively on-line without the time-consuming process of isolation. In addition, 8 phenolic glycosides including 5-hydroxymethylfurfural (HMF), 2-hydroxy-5-(2-hydroxyethyl) phenyl-?-D-glucopyranoside (HPG), anacardoside (ACD), orcinol glucoside (OGD), orcinol-1-O-?-D-apiofuranosyl-(1 ? 6)-?-D-glucopyranoside (OAG), 2,6-dimethoxybenzoic acid (DBA), curculigoside (CUR) and curculigine A (CCL) were quantitated in 11 collected samples and 10 commercial samples from different providers. The results show that UHPLC-ESI-Q-TOF-MS is a viable method for analysis and quality evaluation of the constituents from the rhizome of Curculigo orchioides. PMID:25305598

  15. Analysis of trimethoprim, lincomycin, sulfadoxin and tylosin in swine manure using laser diode thermal desorption-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Solliec, Morgan; Massé, Daniel; Sauvé, Sébastien

    2014-10-01

    A new extraction method coupled to a high throughput sample analysis technique was developed for the determination of four veterinary antibiotics. The analytes belong to different groups of antibiotics such as chemotherapeutics, sulfonamides, lincosamides and macrolides. Trimethoprim (TMP), sulfadoxin (SFX), lincomycin (LCM) and tylosin (TYL) were extracted from lyophilized manure using a sonication extraction. McIlvaine buffer and methanol (MeOH) were used as extraction buffers, followed by cation-exchange solid phase extraction (SPE) for clean-up. Analysis was performed by laser diode thermal desorption-atmospheric pressure chemical-ionization (LDTD-APCI) tandem mass spectrometry (MS/MS) with selected reaction monitoring (SRM) detection. The LDTD is a high throughput sample introduction method that reduces total analysis time to less than 15s per sample, compared to minutes when using traditional liquid chromatography (LC). Various SPE parameters were optimized after sample extraction: the stationary phase, the extraction solvent composition, the quantity of sample extracted and sample pH. LDTD parameters were also optimized: solvent deposition, carrier gas, laser power and corona discharge. The method limit of detection (MLD) ranged from 2.5 to 8.3 µg kg(-1) while the method limit of quantification (MLQ) ranged from 8.3 to 28µgkg(-1). Calibration curves in the manure matrix showed good linearity (R(2)? 0.996) for all analytes and the interday and intraday coefficients of variation were below 14%. Recoveries of analytes from manure ranged from 53% to 69%. The method was successfully applied to real manure samples. PMID:25059125

  16. Measurements of Oxidized Organic Compounds during SOAS 2013 using nitrate ion chemical ionization coupled with High Resolution Time-of-Flight Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Massoli, P.; Stark, H.; Cnagaratna, M.; Junninen, H.; Hakala, J. P.; Mauldin, R.; Ehn, M.; Sipila, M.; Krechmer, J.; Kimmel, J.; Jimenez, J. L.; Jayne, J. T.; Worsnop, D. R.

    2013-12-01

    We present ambient measurements of gaseous organic compounds by means of a High Resolution Time-of-Flight Chemical Ionization Mass Spectrometry (HR-ToF-CIMS) using nitrate ion (NO3-) chemistry. This technique allows to selectively detect oxidized gas-phase species, e.g., oxidized organic molecules and sulfuric acid via clustering with NO3- and its high order clusters. The capability of making such measurements is important because both sulfuric acid and organic gas molecules have a recognized key role in new particle formation (NPF) processes and likely have an important role in particulate phase chemistry and formation of secondary organic aerosols (SOA). The HR-ToF-CIMS was deployed during the Southern Oxidant and Aerosol Study (SOAS) at the forest supersite in Centreville, AL, from June 1 to July 15, 2013. The main goal of the SOAS campaign was to investigate the composition and sources of SOA in the Southeast US, where emissions are mainly represented by biogenic volatile organic compounds (BVOC) emissions and in less extent by anthropogenic emissions (AVOC). During SOAS, the HR-ToF-CIMS detected a range of organic ions that based on previous literature could be identified as oxidation products of both isoprene and terpenes. The isoprene products were 5 to 10 times more abundant than the terpene products. The isoprene-related molecules showed a diurnal cycle with a day time peak, typically after 1500 local time, while the terpene products were higher at night (between 2000 and 0600 local time). These results are consistent with the diurnal trends of primary BVOC emissions from other co-located instruments. The ambient data are also compared to laboratory measurements where oxidized organic vapors are produced using a Potential Aerosol Mass (PAM) flow reactor by the OH oxidation of biogenic gas-phase precursors (isoprene, a-pinene) over multiple days of equivalent atmospheric exposure.

  17. Comprehensive Two Dimensional Gas Chromatography Fast Quadrupole Mass Spectrometry (GC×GC-qMS) for Urinary Steroid Profiling. Mass Spectral Characteristics with Chemical Ionization

    PubMed Central

    Zhang, Ying; Tobias, Herbert J.; Auchus, Richard J.; Brenna, J. Thomas

    2013-01-01

    Comprehensive two dimensional GC (GC×GC), coupled to either a time of flight MS (TOF-MS) or a fast scanning quadrupole MS (qMS) has greatly increased the peak capacity and separation space compared to conventional GC-MS. However, commercial GC×GC-TOFMS systems are not equipped with chemical ionization (CI) and do not provide dominant molecular ions or enable single ion monitoring for maximal sensitivity. A GC×GC-qMS in mass scanning mode was investigated with EI and positive CI (PCI), using CH4 and NH3 as reagent gases. Compared to EI, PCI-NH3 produced more abundant molecular ions and high mass structure specific ions for steroid acetates. Chromatography in two dimensions was optimized with a mixture of 12 endogenous and 3 standard acetylated steroids (SM15-AC) relevant to doping control. Eleven endogenous target steroid acetates were identified in normal urine based on their two retention times, and EI and PCI-NH3 mass spectra; nine of these endogenous target steroid acetates were identified in congenital adrenal hyperplasia (CAH) patients. The difference between the urinary steroids profiles of normal individuals and from a CAH patient can easily be visually distinguished by their GC×GC-qMS chromatograms. We focus here on the comparison and interpretation of the various mass spectra of the targeted endogenous steroids. PCI-NH3 mass spectra were most useful for unambiguous molecular weight determination and for establishing the number of -OH by the losses of 1 or more acetate groups. We conclude that PCI-NH3 with GC×GC-qMS provides improved peak capacity and pseudomolecular ions with structural specificity. PMID:22147458

  18. Three chamber negative ion source

    DOEpatents

    Leung, Ka-Ngo (Hercules, CA); Ehlers, Kenneth W. (Alamo, CA); Hiskes, John R. (Livermore, CA)

    1985-01-01

    A negative ion vessel is divided into an excitation chamber, a negative ionization chamber and an extraction chamber by two magnetic filters. Input means introduces neutral molecules into a first chamber where a first electron discharge means vibrationally excites the molecules which migrate to a second chamber. In the second chamber a second electron discharge means ionizes the molecules, producing negative ions which are extracted into or by a third chamber. A first magnetic filter prevents high energy electrons from entering the negative ionization chamber from the excitation chamber. A second magnetic filter prevents high energy electrons from entering the extraction chamber from the negative ionizing chamber. An extraction grid at the end of the negative ion vessel attracts negative ions into the third chamber and accelerates them. Another grid, located adjacent to the extraction grid, carries a small positive voltage in order to inhibit positive ions from migrating into the extraction chamber and contour the plasma potential. Additional electrons can be suppressed from the output flux using ExB forces provided by magnetic field means and the extractor grid electric potential.

  19. Quantitation of Benzo[a]pyrene Metabolic Profiles in Human Bronchoalveolar H358) Cells by Stable Isotope Dilution Liquid Chromatography-Atmospheric Chemical Ionization Mass Spectrometry

    PubMed Central

    Lu, Ding; Harvey, Ronald G.; Blair, Ian A.; Penning, Trevor M.

    2013-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants and are carcinogenic in multiple organs and species. Benzo[a]pyrene (B[a]P) is a representative PAH and has been studied extensively for its carcinogenicity and toxicity. B[a]P itself is chemically inert and requires metabolic activation to exhibit its toxicity and carcinogenicity. Three major metabolic pathways have been well documented. The signature metabolites generated from the radical cation (peroxidase or monooxygenase mediated) pathway are B[a]P-1,6-dione and B[a]P-3,6-dione, the signature metabolite generated from the diol-epoxide (P450 mediated) pathway is B[a]P-r-7,t-8,t-9,c-10-tetrahydrotetrol (B[a]P-tetrol-1) and the signature metabolite generated from the o-quinone (aldo-keto reductase mediated) pathway is B[a]P-7,8-dione. The contributions of these different metabolic pathways to cancer initiation and the exploitation of this information for cancer prevention are still under debate. With the availability of a library of [13C4]-labeled B[a]P metabolite internal standards, we developed a sensitive stable isotope dilution atmospheric pressure chemical ionization tandem mass spectrometry method to address this issue by quantitating B[a]P metabolites from each metabolic pathway in human lung cells. This analytical method represents a 500 fold increased sensitivity compared with a method using HPLC-radiometric detection. The limit of quantitation (LOQ) was determined to be 6 fmol on column for 3-hydroxybenzo[a]pyrene (3-OH-B[a]P), the generally accepted biomarker for B[a]P exposure. This high level of sensitivity and robustness of the method was demonstrated in a study of B[a]P metabolic profiles in human bronchoalveolar H358 cells induced or uninduced with the AhR ligand, 2,3,7,8-tetrachlorodibenzodioxin (TCDD). All the signature metabolites were detected and successfully quantitated. Our results suggest that all three metabolic pathways contribute equally in the overall metabolism of B[a]P in H358 cells with or without TCDD induction. The sensitivity of the method should permit the identification of cell-type differences in B[a]P activation and detoxication and could also be used for biomonitoring human exposure to PAH. PMID:21962213

  20. Diagnostic ion filtering strategy for chemical characterization of Guge Fengtong Tablet with high-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Zeng, Su-Ling; Liu, Xin-Guang; Lai, Chang-Jiang-Sheng; Liu, E-Hu; Li, Ping

    2015-05-01

    The present study was designed to characterize the chemical constituents of Guge Fengtong Tablet (GGFTT). Based on the chromatographic retention behavior, fragmentation pathways of chemical components and the published literatures, a diagnostic ion filtering strategy with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (HPLC-ESI-Q-TOF/MS) was established to identify the multiple bioactive constituents of GGFTT. The rapid identification of forty-seven components, including 18 phenolic acids, 8 saponins, 14 gingerol-related compounds, and 7 diarylhepatonoids, was accomplished using this newly developed method. The coupling of HPLC-ESI-Q-TOF/MS with the diagnostic ion filtering strategy was useful and efficient for the in-depth structural elucidation of chemical compounds of GGFTT. PMID:25986289

  1. Laser diode thermal desorption atmospheric pressure chemical ionization tandem mass spectrometry applied for the ultra-fast quantitative analysis of BKM120 in human plasma.

    PubMed

    Lanshoeft, Christian; Heudi, Olivier; Leuthold, Luc Alexis; Schlotterbeck, Götz; Elbast, Walid; Picard, Franck; Kretz, Olivier

    2014-09-01

    A sensitive and ultra-fast method utilizing the laser diode thermal desorption ion source using atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS) was developed for the quantitative analysis of BKM120, an investigational anticancer drug in human plasma. Samples originating from protein precipitation (PP) followed by salting-out assisted liquid-liquid extraction (SALLE) were spotted onto the LazWell™ plate prior to their thermal desorption and detection by tandem mass spectrometry in positive mode. The validated method described in this paper presents a high absolute extraction recovery (>90 %) for BKM120 and its internal standard (ISTD) [D8]BKM120, with precision and accuracy meeting the acceptance criteria. Standard curves were linear over the range of 5.00 to 2000 ng mL(-1) with a coefficient of determination (R (2)) >0.995. The method specificity was demonstrated in six different batches of human plasma. Intra- and inter-run precision as well as accuracy within ±20 % at the lower limit of quantification (LLOQ) and ±15 % (other levels) were achieved during a three-run validation for quality control (QC) samples. The post-preparative stability on the LazWell™ plate at room temperature was 72 h and a 200-fold dilution of spiked samples was demonstrated. The method was applied successfully to three clinical studies (n?=?847) and cross-checked with the validated LC-ESI-MS/MS reference method. The sample analysis run time was 10 s as compared to 4.5 min for the current validated LC-ESI-MS/MS method. The resultant data were in agreement with the results obtained using the validated reference LC-ESI-MS/MS assay and the same pharmacokinetic (PK) parameters were calculated for both analytical assays. This work demonstrates that LDTD-APCI-MS/MS is a reliable method for the ultra-fast quantitative analysis of BKM120 which can be used to speed-up and support its bioanalysis in the frame of the clinical trials. PMID:24958346

  2. Hyphenation of Thermal Analysis to Ultrahigh-Resolution Mass Spectrometry (Fourier Transform Ion Cyclotron Resonance Mass Spectrometry) Using Atmospheric Pressure Chemical Ionization For Studying Composition and Thermal Degradation of Complex Materials.

    PubMed

    Rüger, Christopher P; Miersch, Toni; Schwemer, Theo; Sklorz, Martin; Zimmermann, Ralf

    2015-07-01

    In this study, the hyphenation of a thermobalance to an ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometer (UHR FTICR MS) is presented. Atmospheric pressure chemical ionization (APCI) is used for efficient ionization. The evolved gas analysis (EGA), using high-resolution mass spectrometry allows the time-resolved molecular characterization of thermally induced processes in complex materials or mixtures, such as biomass or crude oil. The most crucial part of the setup is the hyphenation between the thermobalance and the APCI source. Evolved gases are forced to enter the atmospheric pressure ionization interface of the MS by applying a slight overpressure at the thermobalance side of the hyphenation. Using the FTICR exact mass data, detailed chemical information is gained by calculation of elemental compositions from the organic species, enabling a time and temperature resolved, highly selective detection of the evolved species. An additional selectivity is gained by the APCI ionization, which is particularly sensitive toward polar compounds. This selectivity on the one hand misses bulk components of petroleum samples such as alkanes and does not deliver a comprehensive view but on the other hand focuses particularly on typical evolved components from biomass samples. As proof of principle, the thermal behavior of different fossil fuels: heavy fuel oil, light fuel oil, and a crude oil, and different lignocellulosic biomass, namely, beech, birch, spruce, ash, oak, and pine as well as commercial available softwood and birch-bark pellets were investigated. The results clearly show the capability to distinguish between certain wood types through their molecular patterns and compound classes. Additionally, typical literature known pyrolysis biomass marker were confirmed by their elemental composition, such as coniferyl aldehyde (C10H10O3), sinapyl aldehyde (C11H12O4), retene (C18H18), and abietic acid (C20H30O2). PMID:26024433

  3. Artifact-Free Quantification of Free 3-Chlorotyrosine, 3-Bromotyrosine, and 3-Nitrotyrosine in Human Plasma by Electron Capture–Negative Chemical Ionization Gas Chromatography Mass Spectrometry and Liquid Chromatography–Electrospray Ionization Tandem Mass Spectrometry

    Microsoft Academic Search

    Joseph P. Gaut; Jaeman Byun; Hung D. Tran; Jay W. Heinecke

    2002-01-01

    Halogenation and nitration of biomolecules have been proposed as key mechanisms of host defense against bacteria, fungi, and viruses. Reactive oxidants also have the potential to damage host tissue, and they have been implicated in disease. In the current studies, we describe specific, sensitive, and quantitative methods for detecting three stable markers of oxidative damage: 3-chlorotyrosine, 3-bromotyrosine, and 3-nitrotyrosine. Our

  4. Triacylglycerols of human milk: Rapid analysis by ammonia negative ion tandem mass spectrometry

    Microsoft Academic Search

    Graeme J. Currie; Heikki Kallio

    1993-01-01

    Human milk traicylglycerols (TAG) were analyzed by ammonia negative ion chemical ionization tandem mass spectrometry. The\\u000a deprotonated molecular ions of triacylglycerols were fractionated at the first mass spectrometry (MS) stage. Twenty-nine of\\u000a the deprotonated TAG ions were further analyzed based on their collisionally activated (CA) spectra. The tandem MS analysis\\u000a covered eleven major acyl carbon number fractions, two of which

  5. Ionization detector

    Microsoft Academic Search

    1978-01-01

    An ionization detecting fire alarm device is disclosed which comprises a double chamber structure, a source disposed in at least one of the chambers, and a vernier adjusting screw electrode protruding into one chamber. The chamber containing the adjustable electrode is more open to the atmosphere than the other chamber. Porting is provided between chambers and detection occurs by sensing

  6. Novel two-step laser ablation and ionization mass spectrometry (2S-LAIMS) of actor-spectator ice layers: Probing chemical composition of D{sub 2}O ice beneath a H{sub 2}O ice layer

    SciTech Connect

    Yang, Rui, E-mail: ryang73@ustc.edu; Gudipati, Murthy S., E-mail: gudipati@jpl.nasa.gov [Science Division, Jet Propulsion Laboratory, California Institute of Technology, Mail Stop 183-301, 4800 Oak Grove Drive, Pasadena, California 91109 (United States)

    2014-03-14

    In this work, we report for the first time successful analysis of organic aromatic analytes imbedded in D{sub 2}O ices by novel infrared (IR) laser ablation of a layered non-absorbing D{sub 2}O ice (spectator) containing the analytes and an ablation-active IR-absorbing H{sub 2}O ice layer (actor) without the analyte. With these studies we have opened up a new method for the in situ analysis of solids containing analytes when covered with an IR laser-absorbing layer that can be resonantly ablated. This soft ejection method takes advantage of the tenability of two-step infrared laser ablation and ultraviolet laser ionization mass spectrometry, previously demonstrated in this lab to study chemical reactions of polycyclic aromatic hydrocarbons (PAHs) in cryogenic ices. The IR laser pulse tuned to resonantly excite only the upper H{sub 2}O ice layer (actor) generates a shockwave upon impact. This shockwave penetrates the lower analyte-containing D{sub 2}O ice layer (spectator, a non-absorbing ice that cannot be ablated directly with the wavelength of the IR laser employed) and is reflected back, ejecting the contents of the D{sub 2}O layer into the vacuum where they are intersected by a UV laser for ionization and detection by a time-of-flight mass spectrometer. Thus, energy is transmitted from the laser-absorbing actor layer into the non-absorbing spectator layer resulting its ablation. We found that isotope cross-contamination between layers was negligible. We also did not see any evidence for thermal or collisional chemistry of PAH molecules with H{sub 2}O molecules in the shockwave. We call this “shockwave mediated surface resonance enhanced subsurface ablation” technique as “two-step laser ablation and ionization mass spectrometry of actor-spectator ice layers.” This method has its roots in the well-established MALDI (matrix assisted laser desorption and ionization) method. Our method offers more flexibility to optimize both the processes—ablation and ionization. This new technique can thus be potentially employed to undertake in situ analysis of materials imbedded in diverse media, such as cryogenic ices, biological samples, tissues, minerals, etc., by covered with an IR-absorbing laser ablation medium and study the chemical composition and reaction pathways of the analyte in its natural surroundings.

  7. Biological aspects of clean-room ionization

    Microsoft Academic Search

    Peter Gefter

    2002-01-01

    Air ionization in clean rooms is expanding. Influence of air ions on biological objects, aerosol status, and charge neutralization should be considered. This paper discusses such biological effects of light ions as ion depletion, bacteria and virus's sterilization, and deodorization. Ion concentration, ion mobility, and chemical composition will be discussed as ways to characterize biological aspects of cleanroom ionization.

  8. Liquid chromatography electrospray tandem mass spectrometric and desorption electrospray ionization tandem mass spectrometric analysis of chemical warfare agents in office media typically collected during a forensic investigation

    Microsoft Academic Search

    P. A. D’Agostino; J. R. Hancock; C. L. Chenier; C. R. Jackson Lepage

    2006-01-01

    Most prior analytical studies have dealt with the determination of chemical warfare agents in environmental or biological matrices that would typically be collected following battlefield use or in support of the Chemical Weapons Convention. These methods may be useful for some investigations, but may not be practical for indoor forensic investigations where chemical warfare agent use is suspected. There is

  9. Negative temperatures and negative dissipation

    Microsoft Academic Search

    Stefan Machlup

    1975-01-01

    Negative absolute temperature, defined in terms of the Boltzmann factor, corresponds to an upside-down energy pyramid. The example of the laser shows population inversion to be accompanied by the switch from absorption to emission, that is, from positive to negative dissipation, from increasing disorder throughout a system to increasing order in a subsystem. Early treatments of the negative-temperature concept are

  10. Treatment of Amaranthus cruentus with chemical and biological inducers of resistance has contrasting effects on fitness and protection against compatible Gram positive and Gram negative bacterial pathogens.

    PubMed

    Casarrubias-Castillo, Kena; Martínez-Gallardo, Norma A; Délano-Frier, John P

    2014-07-01

    Amaranthus cruentus (Ac) plants were treated with the synthetic systemic acquired resistance (SAR) inducer benzothiadiazole (BTH), methyl jasmonate (MeJA) and the incompatible pathogen, Pseudomonas syringae pv. syringae (Pss), under greenhouse conditions. The treatments induced a set of marker genes in the absence of pathogen infection: BTH and Pss similarly induced genes coding for pathogenesis-related and antioxidant proteins, whereas MeJA induced the arginase, LOX2 and amarandin 1 genes. BTH and Pss were effective when tested against the Gram negative pathogen Ps pv. tabaci (Pst), which was found to have a compatible interaction with grain amaranth. The resistance response appeared to be salicylic acid-independent. However, resistance against Clavibacter michiganensis subsp. michiganensis (Cmm), a Gram positive tomato pathogen also found to infect Ac, was only conferred by Pss, while BTH increased susceptibility. Conversely, MeJA was ineffective against both pathogens. Induced resistance against Pst correlated with the rapid and sustained stimulation of the above genes, including the AhPAL2 gene, which were expressed both locally and distally. The lack of protection against Cmm provided by BTH, coincided with a generalized down-regulation of defense gene expression and chitinase activity. On the other hand, Pss-treated Ac plants showed augmented expression levels of an anti-microbial peptide gene and, surprisingly, of AhACCO, an ethylene biosynthetic gene associated with susceptibility to Cmm in tomato, its main host. Pss treatment had no effect on productivity, but compromised growth, whereas MeJA reduced yield and harvest index. Conversely, BTH treatments led to smaller plants, but produced significantly increased yields. These results suggest essential differences in the mechanisms employed by biological and chemical agents to induce SAR in Ac against bacterial pathogens having different infection strategies. This may determine the outcome of a particular plant-pathogen interaction, leading to resistance or susceptibility, as in Cmm-challenged Ac plants previously induced with Pss or BTH, respectively. PMID:24913050

  11. Negative thermal expansion materials

    NASA Astrophysics Data System (ADS)

    Evans, J. S. O.; Mary, T. A.; Sleight, A. W.

    The recent discovery of negative thermal expansion over an unprecedented temperature range in ZrW 2O 8 (which contracts continuously on warming from below 2 K to above 1000 K) has stimulated considerable interest in this unusual phenomenon. Negative and low thermal expansion materials have a number of important potential uses in ceramic, optical and electronic applications. We have now found negative thermal expansion in a large new family of materials with the general formula A 2(MO 4) 3. Chemical substitution dramatically influences the thermal expansion properties of these materials allowing the production of ceramics with negative, positive or zero coefficients of thermal expansion, with the potential to control other important materials properties such as refractive index and dielectric constant. The mechanism of negative thermal expansion and the phase transitions exhibited by this important new class of low-expansion materials will be discussed.

  12. Negative thermal expansion materials

    NASA Astrophysics Data System (ADS)

    Evans, J. S. O.; Mary, T. A.; Sleight, A. W.

    1998-04-01

    The recent discovery of negative thermal expansion over an unprecedented temperature range in ZrW2O8 (which contracts continuously on warming from below 2 K to above 1000 K) has stimulated considerable interest in this unusual phenomenon. Negative and low thermal expansion materials have a number of important potential uses in ceramic, optical and electronic applications. We have now found negative thermal expansion in a large new family of materials with the general formula A2(MO4)3. Chemical substitution dramatically influences the thermal expansion properties of these materials allowing the production of ceramics with negative, positive or zero coefficients of thermal expansion, with the potential to control other important materials properties such as refractive index and dielectric constant. The mechanism of negative thermal expansion and the phase transitions exhibited by this important new class of low-expansion materials will be discussed.

  13. Negative muon chemistry: the quantum muon effect and the finite nuclear mass effect.

    PubMed

    Posada, Edwin; Moncada, Félix; Reyes, Andrés

    2014-10-01

    The any-particle molecular orbital method at the full configuration interaction level has been employed to study atoms in which one electron has been replaced by a negative muon. In this approach electrons and muons are described as quantum waves. A scheme has been proposed to discriminate nuclear mass and quantum muon effects on chemical properties of muonic and regular atoms. This study reveals that the differences in the ionization potentials of isoelectronic muonic atoms and regular atoms are of the order of millielectronvolts. For the valence ionizations of muonic helium and muonic lithium the nuclear mass effects are more important. On the other hand, for 1s ionizations of muonic atoms heavier than beryllium, the quantum muon effects are more important. In addition, this study presents an assessment of the nuclear mass and quantum muon effects on the barrier of He? + H2 reaction. PMID:25188920

  14. Initial results of positron ionization mass spectrometry

    NASA Technical Reports Server (NTRS)

    Donohue, D. L.; Hulett, L. D., Jr.; Mcluckey, S. A.; Glish, G. L.; Eckenrode, B. A.

    1990-01-01

    The use of monoenergetic positrons for the ionization of organic molecules in the gas phase is described. The ionic products are analyzed with a time-of-flight mass spectrometer and detected to produce a mass spectrum. The ionization mechanisms which can be studied in this way include positron impact at energies above the ionization limit of the target molecules, positronium formation in the Ore gap energy range, and positron attachment at energies less than 1eV. The technique of positron ionization mass spectrometry (PIMS) may have analytical utility in that chemical selectivity is observed for one or more of these processes.

  15. Real-time air monitoring of mustard gas and Lewisite 1 by detecting their in-line reaction products by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow ion introduction.

    PubMed

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2015-01-20

    A new method enabling sensitive real-time air monitoring of highly reactive chemical warfare agents, namely, mustard gas (HD) and Lewisite 1 (L1), by detecting ions of their in-line reaction products instead of intact agents, is proposed. The method is based on corona discharge-initiated atmospheric pressure chemical ionization coupled with ion trap tandem mass spectrometry (MS(n)) via counterflow ion introduction. Therefore, it allows for highly sensitive and specific real-time detection of a broad range of airborne compounds. In-line chemical reactions, ionization reactions, and ion fragmentations of these agents were investigated. Mustard gas is oxygenated in small quantity by reactive oxygen species generated in the corona discharge. With increasing air humidity, the MS(2) signal intensity of protonated molecules of mono-oxygenated HD decreases but exceeds that of dominantly existing intact HD. This result can be explained in view of proton affinity. Lewisite 1 is hydrolyzed and oxidized. As the humidity increases from zero, the signal of the final product, namely, didechlorinated, dihydroxylated, and mono-oxygenated L1, quickly increases and reaches a plateau, giving the highest MS(2) and MS(3) signals among those of L1 and its reaction products. The addition of minimal moisture gives the highest signal intensity, even under low humidity. The method was demonstrated to provide sufficient analytical performance to meet the requirements concerning hygienic management and counter-terrorism. It will be the first practical method, in view of sensitivity and specificity, for real-time air monitoring of HD and L1 without sample pretreatment. PMID:25553788

  16. A novel electron source for negative ion mobility spectrometry

    Microsoft Academic Search

    Mahmoud Tabrizchi; Azra Abedi

    2002-01-01

    The possibility of using negative corona discharge in pure nitrogen as the ionization source for negative ion mobility spectrometry (IMS) has been investigated. The discharge in pure nitrogen produces a huge number of electrons, almost 106 times as much as that produced by the conventional 63Ni ionization source. However, this high intensity electron source cannot be simply used in IMS

  17. Recent advancements in sputter-type heavy negative ion sources

    SciTech Connect

    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 ..mu..A 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.

  18. Schinus terebinthifolius scale-up countercurrent chromatography (Part I): High performance countercurrent chromatography fractionation of triterpene acids with off-line detection using atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Vieira, Mariana Neves; Costa, Fernanda das Neves; Leitão, Gilda Guimarães; Garrard, Ian; Hewitson, Peter; Ignatova, Svetlana; Winterhalter, Peter; Jerz, Gerold

    2015-04-10

    'Countercurrent chromatography' (CCC) is an ideal technique for the recovery, purification and isolation of bioactive natural products, due to the liquid nature of the stationary phase, process predictability and the possibility of scale-up from analytical to preparative scale. In this work, a method developed for the fractionation of Schinus terebinthifolius Raddi berries dichloromethane extract was thoroughly optimized to achieve maximal throughput with minimal solvent and time consumption per gram of processed crude extract, using analytical, semi-preparative and preparative 'high performance countercurrent chromatography' (HPCCC) instruments. The method using the biphasic solvent system composed of n-heptane-ethyl acetate-methanol-water (6:1:6:1, v/v/v/v) was volumetrically scaled up to increase sample throughput up to 120 times, while maintaining separation efficiency and time. As a fast and specific detection alternative, the fractions collected from the CCC-separations were injected to an 'atmospheric pressure chemical ionization mass-spectrometer' (APCI-MS/MS) and reconstituted molecular weight MS-chromatograms of the APCI-ionizable compounds from S. terebinthifolius were obtained. This procedure led to the direct isolation of tirucallane type triterpenes such as masticadienonic and 3?-masticadienolic acids. Also oleanonic and moronic acids have been identified for the first time in the species. In summary, this approach can be used for other CCC scale-up processes, enabling MS-target-guided isolation procedures. PMID:25757818

  19. 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

    PubMed Central

    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

  20. A novel reusable ionic liquid chemically bonded fused-silica fiber for headspace solid-phase microextraction/gas chromatography-flame ionization detection of methyl tert-butyl ether in a gasoline sample.

    PubMed

    Amini, Ramin; Rouhollahi, Ahmad; Adibi, Mina; Mehdinia, Ali

    2011-01-01

    A novel ionic liquid (IL) bonded fused-sil-ica fiber for headspace solid-phase microextraction (HS-SPME)/gas chromatography-flame ionization detection (GC-FID) of methyl tert-butyl ether (MTBE) in a gasoline sample was prepared and used. The new proposed chemically bonded fiber has better thermal stability and durability than its corresponding physically coated fiber. Another advantage is that no spacer was used for the purpose of bonding the IL to the surface of the fused-silica. The latter advantage makes the preparation of these fibers easier with lower cost than those prepared using sol-gel method. The ionic liquid 1-methyl-3-(3-trimethoxysilyl propyl) imidazolium bis(trifluoromethylsulfonyl) imide was synthesized and cross linked to the surface of the fused-silica fiber. Then, the chemically IL-modified fibers were applied to the headspace extraction of MTBE. The chemically IL-modified fibers showed improved thermal stability at temperatures up to 220 °C relative to the physically IL-modified fibers (180 °C). The chemically bonded IL film on the surface of the fused-silica fiber was durable over 16 headspace extractions without any significant loss of the IL film. The calibration graph was linear in a concentration range of 2-240 ?g L?¹ (R²=0.996) with the detection limit of 0.1 ?g L?¹ level. The reproducibility (RSD %, n=6) of the new IL bonded fused-silica fiber (8.9%) was better than the physically coated fiber (12%) suggesting that the proposed chemically IL-modified fiber is more robust than the physically IL-modified fiber. The optimum extraction conditions were the followings: 40 °C extraction temperature, 12 min extraction time, 30s desorption time and sample agitation at 200 rpm. PMID:21130999

  1. Production of negative hydrogen ions on metal grids

    NASA Astrophysics Data System (ADS)

    Oohara, W.; Maetani, Y.; Takeda, Takashi; Takeda, Toshiaki; Yokoyama, H.; Kawata, K.

    2015-03-01

    Negative hydrogen ions are produced on a nickel grid with positive-ion irradiation. In order to investigate the production mechanism, a copper grid without the chemisorption of hydrogen atoms and positive helium ions without negative ionization are used for comparison. Positive hydrogen ions reflected on the metal surface obtain two electrons from the surface and become negatively ionized. It is found that the production yield of negative ions by desorption ionization of chemisorbed hydrogen atoms seems to be small, and the production is a minor mechanism.

  2. Comparative investigation of disposition of 3,4-(methylenedioxy)methamphetamine (MDMA) in the rat and the mouse by a capillary gas chromatography-mass spectrometry assay based on perfluorotributylamine-enhanced ammonia positive ion chemical ionization.

    PubMed

    Lim, H K; Zeng, S; Chei, D M; Foltz, R L

    1992-09-01

    A gas chromatography-mass spectrometry assay based on perfluorotributylamine-enhanced ammonia positive ion chemical ionization has been developed for MDMA and three of its primary metabolites in biological specimens; the assay is linear from 2 to 1000 ng ml-1. Quantitatively, more of an administered dose of 10 mg kg-1 MDMA was excreted by the mouse (72%) than by the rat (35%); most in both species was excreted in urine and within 24 h. The difference in per cent excretion is entirely due to proportionally greater excretion of the parent drug by the mouse. 4-Hydroxy-3-methoxymethamphetamine (HMM) is the major urinary metabolite in both species. HMM and another primary metabolite, 4-hydroxy-3-methoxyamphetamine (HMA), were excreted mainly as glucuronide and sulphate conjugates (> 85%). PMID:1363061

  3. The method for on-site determination of trace concentrations of methyl mercaptan and dimethyl sulfide in air using a mobile mass spectrometer with atmospheric pressure chemical ionization, combined with a fast enrichment/separation system.

    PubMed

    Kudryavtsev, Andrey S; Makas, Alexey L; Troshkov, Mikhail L; Grachev, Mikhail ?; Pod'yachev, Sergey P

    2014-06-01

    A method for fast simultaneous on-site determination of methyl mercaptan and dimethyl sulfide in air was developed. The target compounds were actively collected on silica gel, followed by direct flash thermal desorption, fast separation on a short chromatographic column and detection by means of mass spectrometer with atmospheric pressure chemical ionization. During the sampling of ambient air, water vapor was removed with a Nafion selective membrane. A compact mass spectrometer prototype, which was designed earlier at Trofimuk Institute of Petroleum Geology and Geophysics, was used. The minimization of gas load of the atmospheric pressure ion source allowed reducing the power requirements and size of the vacuum system and increasing its ruggedness. The measurement cycle is about 3 min. Detection limits in a 0.6 L sample are 1 ppb for methyl mercaptan and 0.2 ppb for dimethyl sulfide. PMID:24725876

  4. Negative learning

    Microsoft Academic Search

    Michael Oppenheimer; Brian C. O’Neill; Mort Webster

    2008-01-01

    New technical information may lead to scientific beliefs that diverge over time from the a posteriori right answer. We call this phenomenon, which is particularly problematic in the global change arena, negative learning. Negative\\u000a learning may have affected policy in important cases, including stratospheric ozone depletion, dynamics of the West Antarctic\\u000a ice sheet, and population and energy projections. We simulate

  5. Gas phase reactions of electrons, negative ions and free-radicals with transition metal complexes

    NASA Astrophysics Data System (ADS)

    Dillow, Glen William

    1986-11-01

    Negative chemical ionization (NCI) mass spectrometry is used as a probe to examine the negative ion chemistry of metal coordination complexes in the gas phase. Reaction of metal complexes with electrons, nucleophiles, and free-radicals in several NCI plasmas are identified. The first phase details the characterization of (M + CnH2n)(-) and (M + CnH2n + 1)(-) (n=1-5) hydrocarbon adduct ions which are observed at m/z values above the molecular ion, (M)(-), in the methane NCI mass spectra of a variety of metal coordination complexes. In the second and major phase of the project, the reagent gases NF3, CF2Cl2, and CF3Br are used as negative channel chemical ionization reagent gases to generate high abundances of fluoride, chloride, and bromide ions respectively, and the gas phase negative ion chemistry of a variety of metal coordination complexes in the presence of these reagent gases is examined. The NCI mass spectra are reported for the zinc (II) complexes of acetylacetone and its fluorinated analogs, as well as the cobalt (II), nickel (II), copper (II), and zinc (II) complexes of acetylacetone, N,N'-ethylenebis (salicylimine), and meso-tetraphenylporphin. Evidence is presented for the occurrence of a variety of ion/molecule and free radical/molecule processes as well as resonance electron capture.

  6. Effect of moderate heating on the negative electron affinity and photoyield of air-exposed hydrogen-terminated chemical vapor deposited diamond

    E-print Network

    -terminated chemical vapor deposited diamond G. Piantanida, A. Breskin, R. Chechik,a) and O. Katz Department-terminated chemical vapor deposited diamond films was studied in the photon spectral range of 140­210 nm 8.9­5.9 e on the diamond surface is responsible for the observed effect. A simple model is presented for quantitative

  7. Ionization potentials of seaborgium

    Microsoft Academic Search

    E. Johnson; V. Pershina; B. Fricke

    1999-01-01

    Multiconfiguration relativistic Dirac-Fock values were calculated for the first six ionization potentials of seaborgium and of the other group 6 elements. No experimental ionization potentials are available for seaborgium. Accurate experimental values are not available for all of the other ionization potentials. Ionic radii for the 4+ through 6+ ions of seaborgium are also presented. The ionization potentials and ionic

  8. Concerning the ionization of large polyatomic molecules with intense ultrafast lasers

    E-print Network

    Levis, Robert J.

    ionization MPI to tunnel ionization. It is also demonstrated that this structure-based model can yields. This is essential when intense fields are used in detection schemes for chemical dynamics radiation-molecule coupling and the relative ionization prob- abilities in the limit of tunnel ionization

  9. Studies of nanosecond pulse surface ionization wave discharges over solid and liquid dielectric surfaces

    NASA Astrophysics Data System (ADS)

    Petrishchev, Vitaly; Leonov, Sergey; Adamovich, Igor V.

    2014-12-01

    Surface ionization wave discharges generated by high-voltage nanosecond pulses, propagating over a planar quartz surface and over liquid surfaces (distilled water and 1-butanol) have been studied in a rectangular cross section test cell. The discharge was initiated using a custom-made, alternating polarity, high-voltage nanosecond pulse plasma generator, operated at a pulse repetition rate of 100–500 Hz, with a pulse peak voltage and current of 10–15 kV and 7–20 A, respectively, a pulse FWHM of ˜100 ns, and a coupled pulse energy of 2–9 mJ/pulse. Wave speed was measured using a capacitive probe. ICCD camera images demonstrated that the ionization wave propagated predominantly over the quartz wall or over the liquid surface adjacent to the grounded waveguide placed along the bottom wall of the test cell. Under all experimental conditions tested, the surface plasma ‘sheet’ was diffuse and fairly uniform, both for positive and negative polarities. The parameters of ionization wave discharge propagating over distilled water and 1-butanol surfaces were close to those of the discharge over a quartz wall. No perturbation of the liquid surface by the discharge was detected. In most cases, the positive polarity surface ionization wave propagated at a higher speed and over a longer distance compared to the negative polarity wave. For all three sets of experiments (surface ionization wave discharge over quartz, water and 1-butanol), wave speed and travel distance decreased with pressure. Diffuse, highly reproducible surface ionization wave discharge was also observed over the liquid butanol–saturated butanol vapor interface, as well as over the distilled water–saturated water vapor interface, without buffer gas flow. No significant difference was detected between surface ionization discharges sustained using single-polarity (positive or negative), or alternating polarity high-voltage pulses. Plasma emission images yielded preliminary evidence of charge removal from the liquid surface between the pulses on a microsecond time scale. Products of the plasma chemical reaction that accumulated in the ionization wave discharge over the liquid butanol–saturated butanol vapor interface were detected ex situ, using FTIR absorption spectroscopy. Reaction products identified include CO, alkanes (CH4,C2H6, C3H8), alkynes (C2H2), aldehydes (CH2O) and lighter alcohols (CH3OH).

  10. SIMULTANEOUS QUANTIFICATION OF JASMONIC ACID AND SALICYLIC ACID IN PLANTS BY VAPOR PHASE EXTRACTION AND GAS CHROMATOGRAPHY-CHEMICAL IONIZATION-MASS SPECTROMETRY

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Jasmonic acid and salicylic acid represent important signaling compounds in plant defensive responses against other organisms. Here, we present a new method for the easy, sensitive and reproducible quantification of both compounds by vapor phase extraction and gas chromatography-positive ion chemic...

  11. Direct High-Precision Measurements of the (87)Sr/(86)Sr Isotope Ratio in Natural Water without Chemical Separation Using Thermal Ionization Mass Spectrometry Equipped with 10(12) ? Resistors.

    PubMed

    Li, Chao-Feng; Guo, Jing-Hui; Chu, Zhu-Yin; Feng, Lian-Jun; Wang, Xuan-Ce

    2015-07-21

    Thermal ionization mass spectrometry (TIMS) allows excellent precision for determining Sr isotope ratios in natural water samples. Traditionally, a chemical separation procedure using cation exchange resin has been employed to obtain a high purity Sr fraction from natural water, which makes sample preparation time-consuming. In this study, we present a rapid and precise method for the direct determination of the Sr isotope ratio of natural water using TIMS equipped with amplifiers with two 10(12) ? resistors. To eliminate the (87)Rb isobaric interference, Re ribbons are used as filaments, providing a significant advantage over W ribbons in the inhibition of Rb(+) emission, based on systematically examining a series of NIST SRM987 standard doping with various amounts of Rb using Re and W ribbons. To validate the applicability of our method, twenty-two natural water samples, including different water types (rain, snow, river, lake and drinking water), that show a large range in Sr content variations (2.54-922.8 ppb), were collected and analyzed from North and South China. Analytical results show good precision (0.003-0.005%, 2 RSE) and the method was further validated by comparative analysis of the same water with and without chemical separation. The method is simple and rapid, eliminates sample preparation time, and prevents potential contamination during complicated sample-preparation procedures. Therefore, a high sample throughput inherent to the TIMS can be fully utilized. PMID:26105121

  12. Effects of ionizing irradiation and hydrostatic pressure on Escherichia coli O157:H7 inactivation, chemical composition, and sensory acceptability of ground beef patties.

    PubMed

    Schilling, M W; Yoon, Y; Tokarskyy, O; Pham, A J; Williams, R C; Marshall, D L

    2009-04-01

    A randomized complete block design with three replications was utilized to determine the effects of ionizing irradiation and hydrostatic pressure on the inactivation of Escherichia coli O157:H7, volatile composition, and consumer acceptability (n=155) of frozen ground beef patties. E-beam and X-ray irradiation (2kGy) inactivated E. coli O157:H7 below the limit of detection, while hydrostatic pressure treatment (300mPa for 5min at 4°C) did not inactivate this pathogen. Solid-phase microextraction (SPME) was used to extract volatile compounds from treated ground beef patties. Irradiation and hydrostatic pressure altered the volatile composition (P<0.05) of the ground beef patties in respect to radiolytic products. However, results were inconclusive on whether these differences were great enough to use this method to differentiate between irradiated and non-irradiated samples in a commercial setting. Irradiation did not affect (P>0.05) consumer acceptability of ground beef patties when compared to untreated samples, but hydrostatic pressure caused decreased acceptability (P<0.05) when compared to other treatments. PMID:20416567

  13. Negative Messages

    Microsoft Academic Search

    Jurrien Gregor HALFF

    2010-01-01

    Most people think that if we send out a coherent negative message to stakeholders, everything will be fine. But, as Associate Professor Gregor Halff points out, the reality is very different. During a critical situation, there will be more people talking about you than with you.\\u000aHalff shares in this enlightening video that the key to a successful outcome is

  14. Negative-ion formation in the explosives RDX, PETN, and TNT by using the reversal electron attachment detection technique

    NASA Technical Reports Server (NTRS)

    Boumsellek, S.; Alajajian, S. H.; Chutjian, A.

    1992-01-01

    First results of a beam-beam, single-collision study of negative-ion mass spectra produced by attachment of zero-energy electrons to the molecules of the explosives RDX, PETN, and TNT are presented. The technique used is reversal electron attachment detection (READ) wherein the zero-energy electrons are produced by focusing an intense electron beam into a shaped electrostatic field which reverses the trajectory of electrons. The target beam is introduced at the reversal point, and attachment occurs because the electrons have essentially zero longitudinal and radial velocity. The READ technique is used to obtain the 'signature' of molecular ion formation and/or fragmentation for each explosive. Present data are compared with results from atmospheric-pressure ionization and negative-ion chemical ionization methods.

  15. Clonal Isolation of Populations of 7Glutamyl Transpeptidase-positive and -negative Cells from Rat Liver Epithelial Cells Chemically Transformed in Wfro1

    Microsoft Academic Search

    J. W. Grisham; B. B. Chou; J. D. Smith

    In a population of cultured rat liver epithelial cells transformed by 11 brief treatments with \\/V-methyl-N'-nitro-N-nitrosoguani- dine, 9% of the cells stained intensely for 7-glutamyl Iranspepli- dase (GGT). We have isolated from this phenotypically hetero geneous tumorigenic cell population 11 GGT-positive and 7 GGT- negative clonal subpopulations (from single cells) and have ana lyzed the ploidy and selected biochemical, histochemical,

  16. Characteristics of negative-tone chemically amplified resist (MES-EN1G) for 50keV EB mask writing system

    Microsoft Academic Search

    Takehiro Kondoh; Masamitsu Itoh; Toshiyuki Kai

    2002-01-01

    This report shows characteristics of a new negative-tone CAR (MES-EN1G), that we have developed. The CAR is adopted new cross linker that is concentrated more at the bottom of the resist film. The new cross linker raises cross-linking reaction rate at the bottom of resist film. Therefore, undercut profile on chromium film is not observed and vertical resist profile is

  17. Numerical Simulation of the Critical Ionization Velocity Mechanism

    Microsoft Academic Search

    Rodger J. Biasca

    1992-01-01

    The 'critical ionization velocity' (CIV) of a neutral gas is related to a form of anomalous ionization first proposed by Alfven. Although the CIV phenomenon has been verified in laboratory experiments, space-based experiments have provided only inconclusive or negative results as to the existence of CIV in the space environment. If the existence of CIV can be confirmed in space

  18. Aerosol removal by unipolar ionization in indoor environments

    Microsoft Academic Search

    Y. S. Mayya; B. K. Sapra; Arshad Khan; Faby Sunny

    2004-01-01

    Corona discharge based unipolar ionizers are commonly used for reducing aerosol particle concentrations in indoor environments. The ions (usually negative) emitted from the ionizer help in charging the airborne particles, which are then removed from air space by electro-migration effects to the walls of the room due to the space charge induced electric fields. A system of equations has been

  19. Vibronic spectra of jet-cooled 2-aminopurine·H2O clusters studied by UV resonant two-photon ionization spectroscopy and quantum chemical calculations.

    PubMed

    Sinha, Rajeev K; Lobsiger, Simon; Trachsel, Maria; Leutwyler, Samuel

    2011-06-16

    For understanding the major- and minor-groove hydration patterns of DNAs and RNAs, it is important to understand the local solvation of individual nucleobases at the molecular level. We have investigated the 2-aminopurine·H(2)O monohydrate by two-color resonant two-photon ionization and UV/UV hole-burning spectroscopies, which reveal two isomers, denoted A and B. The electronic spectral shift ?? of the S(1) ? S(0) transition relative to bare 9H-2-aminopurine (9H-2AP) is small for isomer A (-70 cm(-1)), while that of isomer B is much larger (?? = -889 cm(-1)). B3LYP geometry optimizations with the TZVP basis set predict four cluster isomers, of which three are doubly H-bonded, with H(2)O acting as an acceptor to a N-H or -NH2 group and as a donor to either of the pyrimidine N sites. The "sugar-edge" isomer A is calculated to be the most stable form with binding energy D(e) = 56.4 kJ/mol. Isomers B and C are H-bonded between the -NH2 group and pyrimidine moieties and are 2.5 and 6.9 kJ/mol less stable, respectively. Time-dependent (TD) B3LYP/TZVP calculations predict the adiabatic energies of the lowest (1)??* states of A and B in excellent agreement with the observed 0(0)(0) bands; also, the relative intensities of the A and B origin bands agree well with the calculated S(0) state relative energies. This allows unequivocal identification of the isomers. The R2PI spectra of 9H-2AP and of isomer A exhibit intense low-frequency out-of-plane overtone and combination bands, which is interpreted as a coupling of the optically excited (1)??* state to the lower-lying (1)n?* dark state. In contrast, these overtone and combination bands are much weaker for isomer B, implying that the (1)??* state of B is planar and decoupled from the (1)n?* state. These observations agree with the calculations, which predict the (1)n?* above the (1)??* state for isomer B but below the (1)??* for both 9H-2AP and isomer A. PMID:21322622

  20. ESTIMATION OF IONIZATION CONSTANTS OF AZO DYES AND RELATED AROMATIC AMINES: ENVIRONMENTAL IMPLICATIONS

    EPA Science Inventory

    Ionization constants for 214 dye molecules were calculated from molecular structures using the chemical reactivity models developed in SPARC (SPARC Performs Automated Reasoning in Chemistry). hese models used fundamental chemical structure theory to predict chemical reactivities ...

  1. Dusty plasma ionization instability with ion drag

    Microsoft Academic Search

    N. D’Angelo

    1998-01-01

    The effect of ion drag on negatively charged dust grains is considered as a possible mechanism of excitation of the dust-acoustic (DA) ionization instability. It is found that DA waves are more and more damped as the coefficient for ion drag, ?, increases from zero to a critical value, ?crit. For ?>?crit a zero-frequency (nonpropagating) perturbation grows when the drag

  2. Improved ultra-performance liquid chromatography with electrospray ionization quadrupole-time-of-flight high-definition mass spectrometry method for the rapid analysis of the chemical constituents of a typical medical formula: Liuwei Dihuang Wan.

    PubMed

    Wang, Ping; Lv, Hai tao; Zhang, Ai hua; Sun, Hui; Yan, Guang li; Han, Ying; Wu, Xiu hong; Wang, Xi jun

    2013-11-01

    Liuwei Dihuang Wan (LDW), a classic Chinese medicinal formula, has been used to improve or restore declined functions related to aging and geriatric diseases, such as impaired mobility, vision, hearing, cognition, and memory. It has attracted increasing attention as one of the most popular and valuable herbal medicines. However, the systematic analysis of the chemical constituents of LDW is difficult and thus has not been well established. In this paper, a rapid, sensitive, and reliable ultra-performance LC with ESI quadrupole TOF high-definition MS method with automated MetaboLynx analysis in positive and negative ion mode was established to characterize the chemical constituents of LDW. The analysis was performed on a Waters UPLC™ HSS T3 using a gradient elution system. MS/MS fragmentation behavior was proposed for aiding the structural identification of the components. Under the optimized conditions, a total of 50 peaks were tentatively characterized by comparing the retention time and MS data. It is concluded that a rapid and robust platform based on ultra-performance LC with ESI quadrupole TOF high-definition MS has been successfully developed for globally identifying multiple constituents of traditional Chinese medicine prescriptions. This is the first report on the systematic analysis of the chemical constituents of LDW. PMID:24039112

  3. Ionization potentials of seaborgium

    SciTech Connect

    Johnson, E.; Pershina, V.; Fricke, B.

    1999-10-21

    Multiconfiguration relativistic Dirac-Fock values were calculated for the first six ionization potentials of seaborgium and of the other group 6 elements. No experimental ionization potentials are available for seaborgium. Accurate experimental values are not available for all of the other ionization potentials. Ionic radii for the 4+ through 6+ ions of seaborgium are also presented. The ionization potentials and ionic radii obtained will be used to predict some physiochemical properties of seaborgium and its compounds.

  4. Ambient Ionization Mass Spectrometry

    Microsoft Academic Search

    Min-Zong Huang; Cheng-Hui Yuan; Sy-Chyi Cheng; Yi-Tzu Cho; Jentaie Shiea

    2010-01-01

    Mass spectrometric ionization methods that operate under ambient conditions and require minimal or no sample pretreatment have attracted much attention in such fields as biomedicine, food safety, antiterrorism, pharmaceuticals, and environmental pollution. These technologies usually involve separate ionization and sample-introduction events, allowing independent control over each set of conditions. Ionization is typically performed under ambient conditions through use of existing

  5. Half-metallic properties, single-spin negative differential resistance, and large single-spin Seebeck effects induced by chemical doping in zigzag-edged graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Yang, Xi-Feng; Zhou, Wen-Qian; Hong, Xue-Kun; Liu, Yu-Shen; Wang, Xue-Feng; Feng, Jin-Fu

    2015-01-01

    Ab initio calculations combining density-functional theory and nonequilibrium Green's function are performed to investigate the effects of either single B atom or single N atom dopant in zigzag-edged graphene nanoribbons (ZGNRs) with the ferromagnetic state on the spin-dependent transport properties and thermospin performances. A spin-up (spin-down) localized state near the Fermi level can be induced by these dopants, resulting in a half-metallic property with 100% negative (positive) spin polarization at the Fermi level due to the destructive quantum interference effects. In addition, the highly spin-polarized electric current in the low bias-voltage regime and single-spin negative differential resistance in the high bias-voltage regime are also observed in these doped ZGNRs. Moreover, the large spin-up (spin-down) Seebeck coefficient and the very weak spin-down (spin-up) Seebeck effect of the B(N)-doped ZGNRs near the Fermi level are simultaneously achieved, indicating that the spin Seebeck effect is comparable to the corresponding charge Seebeck effect.

  6. Qualitative and quantitative analysis of chemical constituents in traditional Chinese medicinal formula Tong-Xie-Yao-Fang by high-performance liquid chromatography/diode array detection/electrospray ionization tandem mass spectrometry.

    PubMed

    Yan, Zhixiang; Yang, Xinghao; Wu, Jianbo; Su, Huai; Chen, Chen; Chen, Yin

    2011-04-01

    Tong-Xie-Yao-Fang (TXYF), a famous traditional Chinese medicine formula, has efficient effects on treatment of the diarrhea-predominant irritable bowel syndrome (D-IBS), a disease with high incidence worldwide. However, the active principles for this complex formula have not been fully explored so far. In this paper, high-performance liquid chromatography coupled with diode array detection and electrospray ionization tandem mass spectrometry (HPLC-DAD-ESI-MS/MS) was applied for the qualitative and quantitative analysis of major chemical constituents in TXYF. Two monoterpene glycosides, one chromone and five polymethoxylated flavones were tentatively characterized based on the retention times, UV spectra and MS data. Fifteen compounds were unambiguously identified by comparison with reference standards. Constituents such as lactone and steroidal, which could not be found by single HPLC method due to the low content in the formula, were identified in this paper. Seven compounds (gallic acid, prim-O-?-D-glucosylcimifugin, paeoniflorin, cimifugin, naringin, hesperidin and 4'-O-?-D-glucosyl-5-O-methylvisamminol) were quantified by HPLC-DAD using a C18 column and gradient elution with acetonitrile and water-0.1% formic acid. The method exhibited intra- and inter-day precision of less than 2.35% and 3.14%, respectively. The LODs and the LOQs for the analytes were less than 0.47 and 1.82 ?g ml(-1), respectively. The overall recoveries ranged from 96.82% to 102.47%, with the R.S.D. ranging from 1.17% to 3.94%. These results demonstrated that our present method was effective and reliable for comprehensive quality evaluation of TXYF. Meanwhile, the study might provide the chemical evidence for revealing the material basis of its therapeutic effects. PMID:21458639

  7. Separation and identification of polar degradation products of benzo[a]pyrene with ozone by atmospheric pressure chemical ionization-mass spectrometry after optimized column chromatographic clean-up.

    PubMed

    Letzel, T; Rosenberg, E; Wissiack, R; Grasserbauer, M; Niessner, R

    1999-09-10

    The environmental relevance of oxidized degradation products of polycyclic aromatic hydrocarbons (PAHs) increases due to enhanced combustion of organic matter and fossil fuels. For PAHs consisting of more than three condensed aromatic rings, soot aerosols are the main carrier, on the surface of which they can react with trace gases like ozone. In this study the clean-up procedure and analysis of ozonized benzo[a]pyrene (B[a]P) was optimized. B[a]P and its degradation products were preseparated into three fractions. Different reversed-phase materials were evaluated for high-performance liquid chromatographic separation. Among these, a phenyl-modified silica material proved best-suited and the chromatographic separation was optimized on this material. For the detection of separated degradation products, liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) was used. With this method, 29 components could be characterized. Besides the three known main degradation products (B[a]P-1,6-dione, B[a]P-3,6-dione, B[a]P-6,12-dione, B[a]P-4,5-dione and 4-oxa-benzo[d,e,f]chrysene-5-one (B[def]C-lactone), were identified for the first time with the help of reference substances. B[def]C-lactone is known as a substance with a mutagenic potential similar to B[a]P. Several other compounds could be tentatively identified. PMID:10519088

  8. Real-time gas and particle-phase organic acids measurement at a forest site using chemical ionization high-resolution time-of-flight mass spectrometry during BEACHON-RoMBAS

    NASA Astrophysics Data System (ADS)

    Yatavelli, L. R.; Stark, H.; Kimmel, J.; Cubison, M.; Day, D. A.; Jayne, J.; Thornton, J. A.; Worsnop, D. R.; Jimenez, J. L.

    2011-12-01

    We present measurement of organic acids in gas and aerosol particles conducted in a ponderosa pine forest during July and August 2011 as part of the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS; http://tinyurl.com/BEACHON-RoMBAS). The measurement technique is based on chemical ionization, high-resolution time-of-flight mass spectrometry and utilizes a Micro-Orifice Volatilization Impactor [MOVI-CI-HR-ToFMS; Yatavelli et al., AS&T, 2010] to collect sub-micron aerosol particles while simultaneously measuring the gas-phase composition. The collected particles are subsequently analyzed by temperature-programmed thermal desorption. The reagent ion chosen for this campaign is the acetate anion (CH3C(O)O-, m/z 59), which reacts selectively via proton transfer with compounds that are stronger gas-phase acids than acetic acid [Veres et al., IJMS, 2008]. Preliminary results show substantial particle-phase concentrations of biogenic oxidation products such as hydroxy-glutaric acid, pinic acid, pinonic acid, and hydroxy-pinonic acid along with numerous lower and higher molecular weight organic acids. Correlations of the organic acid concentrations with meteorological, gas and aerosol parameters measured by other instrumentation are investigated in order to understand the formation, transformation, and partitioning of gas and particle-phase organic acids in a forested environment dominated by terpenes.

  9. Matrix isolation studies of the interactions of BF3 with water and substituted diethyl ethers. Chemical ionization mass spectrometric determination of the proton affinity of (CF3CH2)2O

    NASA Technical Reports Server (NTRS)

    Ball, David W.; Zehe, Michael J.

    1993-01-01

    BF3 was co-condensed with H2O, D2O, (C2H5)2O, (CF3CH2)2O, and (C2F5)2O in excess argon at 15 K. Infrared spectra of BF3/water isolated in solid argon provided a more complete analysis of the BF3--H2O complex than previously published. Infrared spectra of the matrices showed a definite Lewis acid-base interaction between BF3 and diethyl ether; a weak but definite interaction with bis (2,2,2-trifluorodiethyl) ether, and no observable interaction with perfluorodiethyl ether. Thus, the ether data indicate a clear trend between strength of interaction with BF3 and the degree of F substitution. To support and explain the emerging relationship between interaction strength and the basicity of the oxygen-containing molecule, the proton affinity of (CF3CH2)2O was measured using chemical ionization mass spectrometry. The implications of the results for lubricant/metal oxide surface interactions are discussed.

  10. Ionization of NO at high temperature

    NASA Technical Reports Server (NTRS)

    Hansen, C. Frederick

    1991-01-01

    Space vehicles flying through the atmosphere at high speed are known to excite a complex set of chemical reactions in the atmospheric gases, ranging from simple vibrational excitation to dissociation, atom exchange, electronic excitation, ionization, and charge exchange. Simple arguments are developed for the temperature dependence of the reactions leading to ionization of NO, including the effect of vibrational electronic thermal nonequilibrium. NO ionization is the most important source of electrons at intermediate temperatures and at higher temperatures provides the trigger electrons that ionize atoms. Based on these arguments, recommendations are made for formulae which fit observed experimental results, and which include a dependence on both a heavy particle temperature and different vibration electron temperatures. In addition, these expressions will presumably provide the most reliable extrapolation of experimental results to much higher temperatures.

  11. New quantitative structure-fragmentation relationship strategy for chemical structure identification using the calculated enthalpy of formation as a descriptor for the fragments produced in electron ionization mass spectrometry: a case study with tetrachlorinated biphenyls.

    PubMed

    Dinca, Nicolae; Dragan, Simona; Dinca, Mihael; Sisu, Eugen; Covaci, Adrian

    2014-05-20

    Differential mass spectrometry correlated with quantum chemical calculations (QCC-?MS) has been shown to be an efficient tool for the chemical structure identification (CSI) of isomers with similar mass spectra. For this type of analysis, we report here a new strategy based on ordering (ORD), linear correlation (LCOR) algorithms, and their coupling, to filter the most probable structures corresponding to similar mass spectra belonging to a group with dozens of isomers (e.g., tetrachlorinated biphenyls, TeCBs). This strategy quantifies and compares the values of enthalpies of formation (?(f)H) obtained by QCC for some isobaric ions from the electron ionization (EI)-MS mass spectra, to the corresponding relative intensities. The result of CSI is provided in the form of lists of decreasing probabilities calculated for all the position-isomeric structures using the specialized software package CSI-Diff-MS Analysis 3.1.1. The simulation of CSI with ORD, LCOR, and their coupling of six TeCBs (IUPAC no. 44, 46, 52, 66, 74, and 77) has allowed us to find the best semiempirical molecular-orbital methods for several of their common isobaric fragments. The study of algorithms and strategy for the entire group of TeCBs (42 isomers) was made with one of the optimal variants for the computation of ?(f)H using semiempirical molecular orbital methods of HyperChem: AM1 for M(+•) and [M - 4Cl](+•) ions and RM1 for [M - Cl](+) and [M - 2Cl](+•). The analytical performance of ORD, LCOR, and their coupling resulted from the CSI simulation of an analyte of known structure, using a decreasing number of isomeric standards, s = 5, 4, 3, and 2. Compared with the results obtained by a classical library search for TeCB isomers, the novel strategies of assigning structures of isomers with very similar mass spectra based on ORD, LCOR, and their coupling were much more efficient, because they provide the correct structure at the top of the probability list. Databases used in these CSI do not contain mass spectra, as in the case of a library search, but a series of ?(f)H values obtained by QCC. These techniques are capable of relating relative intensities to the chemical structures of analytes via ?(f)H of ions which turns out to be a good quantitative structure-fragmentation relationship (QSFR) descriptor. PMID:24773183

  12. Long-time joint spectra and entanglement of two photoelectrons originating in interacting auto-ionization systems

    E-print Network

    Jan Perina Jr.; A. Luks; W. Leonski

    2015-03-27

    Two auto-ionization systems in a stationary optical field mutually interacting via the dipole-dipole interaction are considered. Their evolution is analytically found. Joint spectra of two ionized electrons are analyzed in detail in the long-time limit for comparable strengths of direct and indirect ionization paths as well as the dominating indirect ionization path. Entanglement in the state of two ionized electrons is quantified using the density of quadratic negativity. Suitable conditions for obtaining highly entangled states are discussed.

  13. IONIZATION IN ATMOSPHERES OF BROWN DWARFS AND EXTRASOLAR PLANETS. V. ALFVÉN IONIZATION

    SciTech Connect

    Stark, C. R.; Helling, Ch.; Rimmer, P. B. [SUPA, School of Physics and Astronomy, University of St Andrews, St Andrews, KY16 9SS (United Kingdom); Diver, D. A., E-mail: craig.stark@st-andrews.ac.uk [SUPA, School of Physics and Astronomy, Kelvin Building, University of Glasgow, Glasgow, G12 8QQ (United Kingdom)

    2013-10-10

    Observations of continuous radio and sporadic X-ray emission from low-mass objects suggest they harbor localized plasmas in their atmospheric environments. For low-mass objects, the degree of thermal ionization is insufficient to qualify the ionized component as a plasma, posing the question: what ionization processes can efficiently produce the required plasma that is the source of the radiation? We propose Alfvén ionization as a mechanism for producing localized pockets of ionized gas in the atmosphere, having sufficient degrees of ionization (?10{sup –7}) that they constitute plasmas. We outline the criteria required for Alfvén ionization and demonstrate its applicability in the atmospheres of low-mass objects such as giant gas planets, brown dwarfs, and M dwarfs with both solar and sub-solar metallicities. We find that Alfvén ionization is most efficient at mid to low atmospheric pressures where a seed plasma is easier to magnetize and the pressure gradients needed to drive the required neutral flows are the smallest. For the model atmospheres considered, our results show that degrees of ionization of 10{sup –6}-1 can be obtained as a result of Alfvén ionization. Observable consequences include continuum bremsstrahlung emission, superimposed with spectral lines from the plasma ion species (e.g., He, Mg, H{sub 2}, or CO lines). Forbidden lines are also expected from the metastable population. The presence of an atmospheric plasma opens the door to a multitude of plasma and chemical processes not yet considered in current atmospheric models. The occurrence of Alfvén ionization may also be applicable to other astrophysical environments such as protoplanetary disks.

  14. Low-density ionization behavior

    SciTech Connect

    Baker, G.A. Jr.

    1995-04-01

    As part of a continuing study of the physics of matter under extreme conditions, I give some results on matter at extremely low density. In particular I compare a quantum mechanical calculation of the pressure for atomic hydrogen with the corresponding pressure given by Thomas-Fermi theory. (This calculation differs from the ``confined atom`` approximation in a physically significant way.) Since Thomas-Fermi theory in some sense, represents the case of infinite nuclear charge, these cases should represent extremes. Comparison is also made with Saha theory, which considers ionization from a chemical point of view, but is weak on excited-state effects. In this theory, the pressure undergoes rapid variation as electron ionization levels are passed. This effect is in contrast to the smooth behavior of the Thomas-Fermi fixed temperature, complete ionization occurs in the low density limit, I study the case where the temperature goes appropriately to zero with the density. Although considerable modification is required, Saha theory is closer to the actual results for this case than is Thomas-Fermi theory.

  15. Dispersive liquid-liquid microextraction for the determination of vitamins D and K in foods by liquid chromatography with diode-array and atmospheric pressure chemical ionization-mass spectrometry detection.

    PubMed

    Viñas, Pilar; Bravo-Bravo, María; López-García, Ignacio; Hernández-Córdoba, Manuel

    2013-10-15

    A simple and rapid method was developed using reversed-phase liquid chromatography (LC) with both diode array (DAD) and atmospheric pressure chemical ionization mass spectrometric (APCI-MS) detection, for the simultaneous analysis of the vitamins ergocalciferol (D2), cholecalciferol (D3), phylloquinone (K1), menaquinone-4 (K2) and a synthetic form of vitamin K, menadione (K3). The Taguchi experimental method, an orthogonal array design (OAD), was used to optimize an efficient and clean preconcentration step based on dispersive liquid-liquid microextraction (DLLME). A factorial design was applied with six factors and three levels for each factor, namely, carbon tetrachloride volume, methanol volume, aqueous sample volume, pH of sample, sodium chloride concentration and time of the centrifugation step. The DLLME optimized procedure consisted of rapidly injecting 3 mL of acetonitrile (disperser solvent) containing 150 µL carbon tetrachloride (extraction solvent) into the aqueous sample, thereby forming a cloudy solution. Phase separation was performed by centrifugation, and the sedimented phase was evaporated with nitrogen, reconstituted with 50 µL of acetonitrile, and injected. The LC analyses were carried out using a mobile phase composed of acetonitrile, 2-propanol and water, under gradient elution. Quantification was carried out by the standard additions method. The APCI-MS spectra, in combination with UV spectra, permitted the correct identification of compounds in the food samples. The method was validated according to international guidelines and using a certified reference material. The validated method was applied for the analysis of vitamins D and K in infant foods and several green vegetables. There was little variability in the forms of vitamin K present in vegetables, with the most abundant vitamer in all the samples being phylloquinone, while menadione could not be detected. Conversely, cholecalciferol, which is present in food of animal origin, was the main form in infant foods, while ergocalciferol was not detected. PMID:24054666

  16. Development of a new multi-residue laser diode thermal desorption atmospheric pressure chemical ionization tandem mass spectrometry method for the detection and quantification of pesticides and pharmaceuticals in wastewater samples.

    PubMed

    Boisvert, Michel; Fayad, Paul B; Sauvé, Sébastien

    2012-11-19

    A new solid phase extraction (SPE) method coupled to a high throughput sample analysis technique was developed for the simultaneous determination of nine selected emerging contaminants in wastewater (atrazine, desethylatrazine, 17?-estradiol, ethynylestradiol, norethindrone, caffeine, carbamazepine, diclofenac and sulfamethoxazole). We specifically included pharmaceutical compounds from multiple therapeutic classes, as well as pesticides. Sample pre-concentration and clean-up was performed using a mixed-mode SPE cartridge (Strata ABW) having both cation and anion exchange properties, followed by analysis by laser diode thermal desorption atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). The LDTD interface is a new high-throughput sample introduction method, which reduces total analysis time to less than 15s per sample as compared to minutes with traditional liquid-chromatography coupled to tandem mass spectrometry (LC-MS/MS). Several SPE parameters were evaluated in order to optimize recovery efficiencies when extracting analytes from wastewater, such as the nature of the stationary phase, the loading flow rate, the extraction pH, the volume and composition of the washing solution and the initial sample volume. The method was successfully applied to real wastewater samples from the primary sedimentation tank of a municipal wastewater treatment plant. Recoveries of target compounds from wastewater ranged from 78% to 106%, the limit of detection ranged from 30 to 122ng L(-1) while the limit of quantification ranged from 90 to 370ng L(-1). Calibration curves in the wastewater matrix showed good linearity (R(2)?0.991) for all target analytes and the intraday and interday coefficient of variation was below 15%, reflecting a good precision. PMID:23140957

  17. Identification of chemical warfare agents from vapor samples using a field-portable capillary gas chromatography/membrane-interfaced electron ionization quadrupole mass spectrometry instrument with Tri-Bed concentrator.

    PubMed

    Nagashima, Hisayuki; Kondo, Tomohide; Nagoya, Tomoki; Ikeda, Toru; Kurimata, Naoko; Unoke, Shohei; Seto, Yasuo

    2015-08-01

    A field-portable gas chromatograph-mass spectrometer (Hapsite ER system) was evaluated for the detection of chemical warfare agents (CWAs) in the vapor phase. The system consisted of Tri-Bed concentrator gas sampler (trapping time: 3s(-1)min), a nonpolar low thermal-mass capillary gas chromatography column capable of raising temperatures up to 200°C, a hydrophobic membrane-interfaced electron ionization quadrupole mass spectrometer evacuated by a non-evaporative getter pump for data acquisition, and a personal computer for data analysis. Sample vapors containing as little as 22?g sarin (GB), 100?g soman (GD), 210?g tabun (GA), 55?g cyclohexylsarin (GF), 4.8?g sulfur mustard, 390?g nitrogen mustard 1, 140?g of nitrogen mustard 2, 130?g nitrogen mustard 3, 120?g of 2-chloroacetophenone and 990?g of chloropicrin per cubic meter could be confirmed after Tri-Bed micro-concentration (for 1min) and automated AMDIS search within 12min. Using manual deconvolution by background subtraction of neighboring regions on the extracted ion chromatograms, the above-mentioned CWAs could be confirmed at lower concentration levels. The memory effects were also examined and we found that blister agents showed significantly more carry-over than nerve agents. Gasoline vapor was found to interfere with the detection of GB and GD, raising the concentration limits for confirmation in the presence of gasoline by both AMDIS search and manual deconvolution; however, GA and GF were not subject to interference by gasoline. Lewisite 1, and o-chlorobenzylidene malononitrile could also be confirmed by gas chromatography, but it was hard to quantify them. Vapors of phosgene, chlorine, and cyanogen chloride could be confirmed by direct mass spectrometric detection at concentration levels higher than 2, 140, and 10mg/m(3) respectively, by bypassing the micro-concentration trap and gas chromatographic separation. PMID:26118803

  18. Analytical instruments, ionization sources, and ionization methods

    DOEpatents

    Atkinson, David A.; Mottishaw, Paul

    2006-04-11

    Methods and apparatus for simultaneous vaporization and ionization of a sample in a spectrometer prior to introducing the sample into the drift tube of the analyzer are disclosed. The apparatus includes a vaporization/ionization source having an electrically conductive conduit configured to receive sample particulate which is conveyed to a discharge end of the conduit. Positioned proximate to the discharge end of the conduit is an electrically conductive reference device. The conduit and the reference device act as electrodes and have an electrical potential maintained between them sufficient to cause a corona effect, which will cause at least partial simultaneous ionization and vaporization of the sample particulate. The electrical potential can be maintained to establish a continuous corona, or can be held slightly below the breakdown potential such that arrival of particulate at the point of proximity of the electrodes disrupts the potential, causing arcing and the corona effect. The electrical potential can also be varied to cause periodic arcing between the electrodes such that particulate passing through the arc is simultaneously vaporized and ionized. The invention further includes a spectrometer containing the source. The invention is particularly useful for ion mobility spectrometers and atmospheric pressure ionization mass spectrometers.

  19. Tandem Mass Spectrometry of Heparan Sulfate Negative Ions: Sulfate Loss Patterns and Chemical Modification Methods for Improvement of Product Ion Profiles

    NASA Astrophysics Data System (ADS)

    Shi, Xiaofeng; Huang, Yu; Mao, Yang; Naimy, Hicham; Zaia, Joseph

    2012-09-01

    Heparan sulfate (HS) is a polysaccharide modified with sulfation, acetylation, and epimerization that enable its binding with protein ligands and regulation of important biological processes. Tandem mass spectrometry has been employed to sequence linear biomolecules e.g., proteins and peptides. However, its application in structural characterization of HS is limited due to the neutral loss of sulfate (SO3) during collisional induced dissociation (CID). In this report, we studied the dissociation patterns of HS disaccharides and demonstrate that the N-sulfate (N-S) bond is especially facile during CID. We identified factors that influence the propensities of such losses from precursor ions and proposed a Free Proton Index (FPI) to help select ions that are able to produce meaningful backbone dissociations. We then investigated the thermodynamics and kinetics of SO3 loss from sulfates that are protonated, deprotonated, and metal-adducted using density functional theory computations. The calculations showed that sulfate loss from a protonated site was much more facile than that from a deprotonated or metal-adducted site. Further, the loss of SO3 from N-sulfate was energetically favored by 3-8 kcal/mol in transition states relative to O-sulfates, making it more prone to this process by a substantial factor. In order to reduce the FPI, representing the number of labile sulfates in HS native chains and oligosaccharides, we developed a series of chemical modifications to selectively replace the N-sulfates of the glucosamine with deuterated acetyl group. These modifications effectively reduced the sulfate density on the HS oligosaccharides and generated considerably more backbone dissociation using on-line LC/tandem MS.

  20. Laser Ablation Electrospray Ionization for Atmospheric Pressure, in Vivo, and Imaging Mass

    E-print Network

    Vertes, Akos

    Laser Ablation Electrospray Ionization for Atmospheric Pressure, in Vivo, and Imaging Mass. For example, atmospheric pressure infrared MALDI (AP IR-MALDI), capable of producing ions from small ionization (DESI),5 desorption atmospheric pressure chemical ionization (DAPCI),6 and matrix- assisted laser

  1. The critical ionization velocity

    Microsoft Academic Search

    M. A. Raadu

    1980-01-01

    The critical ionization velocity effect is discussed in the context of space plasmas. This effect occurs for a neutral gas moving through a magnetized plasma and leads to rapid ionization and braking of the relative motion when a certain marginal velocity, the critical velocity, is exceeded. Laboratory experiments clearly establish the significance of the critical velocity and provide evidence for

  2. Strong Ionizing Shock Waves

    Microsoft Academic Search

    Robert A. Gross

    1965-01-01

    The physical effects created by strong shock waves propagating in hydrogen are reviewed and theoretically studied for speeds up to relativistic conditions. In the progression from weak to relativistic shock speeds, various physical phenomena affect the shock wave. Dissociation, ionization, and the presence of an upstream electric field cause several important effects for slow (sub-Alfvénic speed) normal ionizing shock waves.

  3. Negative Chemotaxis in Escherichia coli

    PubMed Central

    Tso, Wung-Wai; Adler, Julius

    1974-01-01

    Several methods for detecting or measuring negative chemotaxis are described. Using these, we have surveyed a number of chemicals for their ability to repel Escherichia coli. Although most of the repellents are harmful compounds, harmfulness is neither necessary nor sufficient to make a compound a repellent. The repellents can be grouped into at least nine classes according to (i) competition experiments, (ii) mutants lacking certain of the negative taxes, and (iii) their chemical structure. The specificity of each class was studied. It is suggested that each class corresponds to a distinct chemoreceptor. Generally, non-chemotactic mutants lack both positive and negative chemotaxis, and l-methionine is required for both kinds of taxis. Repellents at very low concentrations are not attractants, and attractants at very high concentrations are not repellents. Images PMID:4597449

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

    Microsoft Academic Search

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

    2002-01-01

    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

  5. Matrix Assisted Ionization in Vacuum, a Sensitive and Widely Applicable Ionization Method for Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Trimpin, Sarah; Inutan, Ellen D.

    2013-05-01

    An astonishingly simple new method to produce gas-phase ions of small molecules as well as proteins from the solid state under cold vacuum conditions is described. This matrix assisted ionization vacuum (MAIV) mass spectrometry (MS) method produces multiply charged ions similar to those that typify electrospray ionization (ESI) and uses sample preparation methods that are nearly identical to matrix-assisted laser desorption/ionization (MALDI). Unlike these established methods, MAIV does not require a laser or voltage for ionization, and unlike the recently introduced matrix assisted ionization inlet method, does not require added heat. MAIV-MS requires only introduction of a crystalline mixture of the analyte incorporated with a suitable small molecule matrix compound such as 3-nitrobenzonitrile directly to the vacuum of the mass spectrometer. Vacuum intermediate pressure MALDI sources and modified ESI sources successfully produce ions for analysis by MS with this method. As in ESI-MS, ion formation is continuous and, without a laser, little chemical background is observed. MAIV, operating from a surface offers the possibility of significantly improved sensitivity relative to atmospheric pressure ionization because ions are produced in the vacuum region of the mass spectrometer eliminating losses associated with ion transfer from atmospheric pressure to vacuum. Mechanistic aspects and potential applications for this new ionization method are discussed.

  6. Measurement of the first ionization potential of astatine by laser ionization spectroscopy

    PubMed Central

    Rothe, S.; Andreyev, A. N.; Antalic, S.; Borschevsky, A.; Capponi, L.; Cocolios, T. E.; De Witte, H.; Eliav, E.; Fedorov, D. V.; Fedosseev, V. N.; Fink, D. A.; Fritzsche, S.; Ghys, L.; Huyse, M.; Imai, N.; Kaldor, U.; Kudryavtsev, Yuri; Köster, U.; Lane, J. F. W.; Lassen, J.; Liberati, V.; Lynch, K. M.; Marsh, B. A.; Nishio, K.; Pauwels, D.; Pershina, V.; Popescu, L.; Procter, T. J.; Radulov, D.; Raeder, S.; Rajabali, M. M.; Rapisarda, E.; Rossel, R. E.; Sandhu, K.; Seliverstov, M. D.; Sjödin, A. M.; Van den Bergh, P.; Van Duppen, P.; Venhart, M.; Wakabayashi, Y.; Wendt, K. D. A.

    2013-01-01

    The radioactive element astatine exists only in trace amounts in nature. Its properties can therefore only be explored by study of the minute quantities of artificially produced isotopes or by performing theoretical calculations. One of the most important properties influencing the chemical behaviour is the energy required to remove one electron from the valence shell, referred to as the ionization potential. Here we use laser spectroscopy to probe the optical spectrum of astatine near the ionization threshold. The observed series of Rydberg states enabled the first determination of the ionization potential of the astatine atom, 9.31751(8) eV. New ab initio calculations are performed to support the experimental result. The measured value serves as a benchmark for quantum chemistry calculations of the properties of astatine as well as for the theoretical prediction of the ionization potential of superheavy element 117, the heaviest homologue of astatine. PMID:23673620

  7. Measurement of the first ionization potential of astatine by laser ionization spectroscopy

    NASA Astrophysics Data System (ADS)

    Rothe, S.; Andreyev, A. N.; Antalic, S.; Borschevsky, A.; Capponi, L.; Cocolios, T. E.; de Witte, H.; Eliav, E.; Fedorov, D. V.; Fedosseev, V. N.; Fink, D. A.; Fritzsche, S.; Ghys, L.; Huyse, M.; Imai, N.; Kaldor, U.; Kudryavtsev, Yuri; Köster, U.; Lane, J. F. W.; Lassen, J.; Liberati, V.; Lynch, K. M.; Marsh, B. A.; Nishio, K.; Pauwels, D.; Pershina, V.; Popescu, L.; Procter, T. J.; Radulov, D.; Raeder, S.; Rajabali, M. M.; Rapisarda, E.; Rossel, R. E.; Sandhu, K.; Seliverstov, M. D.; Sjödin, A. M.; van den Bergh, P.; van Duppen, P.; Venhart, M.; Wakabayashi, Y.; Wendt, K. D. A.

    2013-05-01

    The radioactive element astatine exists only in trace amounts in nature. Its properties can therefore only be explored by study of the minute quantities of artificially produced isotopes or by performing theoretical calculations. One of the most important properties influencing the chemical behaviour is the energy required to remove one electron from the valence shell, referred to as the ionization potential. Here we use laser spectroscopy to probe the optical spectrum of astatine near the ionization threshold. The observed series of Rydberg states enabled the first determination of the ionization potential of the astatine atom, 9.31751(8) eV. New ab initio calculations are performed to support the experimental result. The measured value serves as a benchmark for quantum chemistry calculations of the properties of astatine as well as for the theoretical prediction of the ionization potential of superheavy element 117, the heaviest homologue of astatine.

  8. Measurement of the first ionization potential of astatine by laser ionization spectroscopy

    E-print Network

    Rothe, S; Antalic, S; Borschevsky, A; Capponi, L; Cocolios, T E; De Witte, H; Eliav, E; Fedorov, D V; Fedosseev, V N; Fink, D A; Fritzsche, S; Ghys, L; Huyse, M; Imai, N; Kaldor, U; Kudryavtsev, Yu; Köster, U; Lane, J; Lassen, J; Liberati, V; Lynch, K M; Marsh, B A; Nishio, K; Pauwels, D; Pershina, V; Popescu, L; Procter, T J; Radulov, D; Raeder, S; Rajabali, M M; Rapisarda, E; Rossel, R E; Sandhu, K; Seliverstov, M D; Sjödin, A M; Van den Bergh, P; Van Duppen, P; Venhart, M; Wakabayashi, Y; Wendt K D A

    2013-01-01

    The radioactive element astatine exists only in trace amounts in nature. Its properties can therefore only be explored by study of smallest quantities of artificially produced isotopes or by performing theoretical calculations. One of the most important properties influencing the chemical behaviour is the energy required to remove one electron from the valence shell, referred to as the ionization potential. Here we use laser spectroscopy to probe the optical spectrum of astatine near the ionization threshold. The observed series of Rydberg states enabled the first determination of the ionization potential of the astatine atom, 9.317510(8) eV. New ab initio calculations were performed to support the experimental result. The measured value serves as a benchmark for quantum chemistry calculations of the properties of astatine as well as for the theoretical prediction of the ionization potential of super-heavy element 117, the heaviest homologue of astatine.

  9. Measurement of the first ionization potential of astatine by laser ionization spectroscopy.

    PubMed

    Rothe, S; Andreyev, A N; Antalic, S; Borschevsky, A; Capponi, L; Cocolios, T E; De Witte, H; Eliav, E; Fedorov, D V; Fedosseev, V N; Fink, D A; Fritzsche, S; Ghys, L; Huyse, M; Imai, N; Kaldor, U; Kudryavtsev, Yuri; Köster, U; Lane, J F W; Lassen, J; Liberati, V; Lynch, K M; Marsh, B A; Nishio, K; Pauwels, D; Pershina, V; Popescu, L; Procter, T J; Radulov, D; Raeder, S; Rajabali, M M; Rapisarda, E; Rossel, R E; Sandhu, K; Seliverstov, M D; Sjödin, A M; Van den Bergh, P; Van Duppen, P; Venhart, M; Wakabayashi, Y; Wendt, K D A

    2013-01-01

    The radioactive element astatine exists only in trace amounts in nature. Its properties can therefore only be explored by study of the minute quantities of artificially produced isotopes or by performing theoretical calculations. One of the most important properties influencing the chemical behaviour is the energy required to remove one electron from the valence shell, referred to as the ionization potential. Here we use laser spectroscopy to probe the optical spectrum of astatine near the ionization threshold. The observed series of Rydberg states enabled the first determination of the ionization potential of the astatine atom, 9.31751(8) eV. New ab initio calculations are performed to support the experimental result. The measured value serves as a benchmark for quantum chemistry calculations of the properties of astatine as well as for the theoretical prediction of the ionization potential of superheavy element 117, the heaviest homologue of astatine. PMID:23673620

  10. Capillary gas chromatography with chemical ionization negative ion mass spectrometry in the identification of odorous steroids formed in metabolic studies of the sulphates of androsterone, DHA and 5?-androst-16-en-3?-ol with human axillary bacterial isolates

    Microsoft Academic Search

    D. B. Gower; A. I. Mallet; W. J. Watkins; L. M. Wallace; J.-P. Calame

    1997-01-01

    The products of metabolism of the sulphates (0.5 ?mol\\/l) of androsterone, dehydroepiandrosterone (DHA) and 5?-androst-16-en-3?-ol have been investigated after incubation with 72 h cultures of human axillary bacterial isolates for 3 days at 37°C. The medium used, tryptone soya broth (TSB), contained yeast extract and Tween 80. The isolates used were Coryneform F1 (known previously to metabolize testosterone and to

  11. Trace level determination of organochlorine, organophosphorus and pyrethroid pesticides in lanolin using gel permeation chromatography followed by dual gas chromatography and gas chromatography–negative chemical ionization mass spectrometric confirmation

    Microsoft Academic Search

    Eric Jover; Josep Maria Bayona

    2002-01-01

    A methodology for multi-class pesticide determination at trace level in lanolin is presented. Gel permeation chromatography on a Bio-Beads SX-3 column followed by a dual GC chromatographic determination has been developed. The effluent of the analytical column (50% diphenyl–methyl- or 14% cyanopropyl–phenylpolysiloxane) was split into an electron-capture and a nitrogen–phosphorus detection system. The chromatographic system was optimised for 28 pesticides

  12. QUANTITATION OF ESTROGENS IN GROUND WATER AND SWINE LAGOON SAMPLE USING SOLID PHASE EXTRACTION, PENTAFLUROBENZYL/TRIMETHYLSILYL DERIVATIZATIONS AND GAS CHROMATOGRAPHY NEGATIVE ION CHEMICAL IONIZATION/MASS SPECTROMETRY/MASS SPECTROMETRY

    EPA Science Inventory

    A method was developed for the confirmed identification and quantitation of 17B-estradiol, estrone, 17B-ethynylestrodial and 16a-hydroxy-17B-estradiol (estriol) in ground water and swine lagoon samples. Centrifuged and filtered samples were extracted using solid phase extraction...

  13. Drug Testing in Blood: Validated Negative-Ion Chemical Ionization Gas Chromatographic-Mass Spectrometric Assay for Determination of Amphetamine and Methamphetamine Enantiomers and Its Application to Toxicology Cases

    Microsoft Academic Search

    Frank T. Peters; Thomas Kraemer; Hans H. Maurer

    Background: Enantioselective analysis of amphetamine (AM) or methamphetamine (MA) in urine is already a well-established tool for differentiation of illicit from therapeutic ingestion of AM or MA derivatives. How- ever, because of the increasing importance of plasma or serum in analytical toxicology, a method for enantiose- lective analysis of AM and MA in these matrices is needed. Methods: AM and\\/or

  14. Dusty plasma ionization instability with ion drag

    Microsoft Academic Search

    N. D'Angelo

    1998-01-01

    The effect of ion drag on negatively charged dust grains is considered as a possible mechanism of excitation of the dust-acoustic (DA) ionization instability. It is found that DA waves are more and more damped as the coefficient for ion drag, mu, increases from zero to a critical value, mucrit. For mu>mucrit a zero-frequency (nonpropagating) perturbation grows when the drag

  15. Abnormal ionization in sonoluminescence

    NASA Astrophysics Data System (ADS)

    Zhang, Wen-Juan; An, Yu

    2015-04-01

    Sonoluminescence is a complex phenomenon, the mechanism of which remains unclear. The present study reveals that an abnormal ionization process is likely to be present in the sonoluminescing bubble. To fit the experimental data of previous studies, we assume that the ionization energies of the molecules and atoms in the bubble decrease as the gas density increases and that the decrease of the ionization energy reaches about 60%–70% as the bubble flashes, which is difficult to explain by using previous models. Project supported by the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20120002110031) and the National Natural Science Foundation of China (Grant No. 11334005).

  16. Fragmentation pathways of ethylene after core ionization

    NASA Astrophysics Data System (ADS)

    Gaire, B.; Bocharova, I.; Sturm, F. P.; Gehrken, N.; Haxton, D. J.; Belkacem, A.; Weber, Th.; Zohrabi, M.; Ben-Itzhak, I.; Gatton, A.; Williams, J.; Reedy, D.; Nook, C.; Landers, A.; Gassert, H.; Zeller, S.; Voigtsberger, J.; Jahnke, T.; Doerner, R.

    2014-05-01

    We have measured the Auger electrons in coincidence with the recoil ions, resulting from the core ionization of ethylene molecules, by employing the COLd Target Recoil Ion Momentum Spectroscopy (COLTRIMS) method. The Auger-electron and recoil-ion energy maps are used to identify the fragmentation pathways and they are compared to the valence photo-double-ionization of ethylene. The dicationic electronic states favored by the propensity rules are identified and their role on the fragmentation pathways is discussed. The molecular-frame Auger electron angular distribution provides further insight into the breakup of this molecule after core ionization. Supported by the Director, Office of Science, Office of Basic Energy Sciences, and by the Division of Chemical Sciences, Geosciences, and Biosciences of the U.S. Department of Energy at LBNL under Contract No. DE-AC02-05CH11231.

  17. Optimization of plasma ionization sources for ambient mass spectrometry surface analysis

    NASA Astrophysics Data System (ADS)

    McKay, Kirsty; Oh, Jun-Seok; Bowfield, Andrew; Salter, Tara; Walsh, James; Gilmore, Ian; Bradley, James

    2013-09-01

    The use of low-temperature atmospheric pressure plasma sources in ambient surface analysis mass spectrometry has received growing interest in recent years. Due to their unique chemical and electrical properties plasmas provide a gentle and efficient means of ionizing surface compounds in their natural environment, with little to no sample preparation required. In this study we investigate how these plasma ionization sources might be optimized for ambient surface analysis techniques. An ambient molecular beam mass spectrometer from Hiden Analytical Ltd. (HPR-60) is used to monitor the charged ion species emanating from two different plasma sources, a pulse modulated RF (13.56 MHz) plasma needle and a continuous wave kHz plasma jet, under different operating parameters. Both time-averaged and time-resolved ion intensity measurements reveal the species present in the discharges and the underlying production and loss mechanisms for different operating conditions. To assess the effectiveness of each of these plasmas sources as tools for surface ionization/desorption, a number of different pharmaceutical and polymer surfaces were analyzed in both positive and negative ion mode using a hybrid linear trap quadrupole (LTQ) orbitrap mass spectrometer, due to its increased mass sensitivity.

  18. Ionizing potential waves and high-voltage breakdown streamers.

    NASA Technical Reports Server (NTRS)

    Albright, N. W.; Tidman, D. A.

    1972-01-01

    The structure of ionizing potential waves driven by a strong electric field in a dense gas is discussed. Negative breakdown waves are found to propagate with a velocity proportional to the electric field normal to the wavefront. This causes a curved ionizing potential wavefront to focus down into a filamentary structure, and may provide the reason why breakdown in dense gases propagates in the form of a narrow leader streamer instead of a broad wavefront.

  19. Negative ion source with hollow cathode discharge plasma

    DOEpatents

    Hershcovitch, A.; Prelec, K.

    1980-12-12

    A negative ion source of the type where negative ions are formed by bombarding a low-work-function surface with positive ions and neutral particles from a plasma, wherein a highly ionized plasma is injected into an anode space containing the low-work-function surface is described. The plasma is formed by hollow cathode discharge and injected into the anode space along the magnetic field lines. Preferably, the negative ion source is of the magnetron type.

  20. Negative ion source with hollow cathode discharge plasma

    DOEpatents

    Hershcovitch, Ady (Mt. Sinai, NY); Prelec, Krsto (Setauket, NY)

    1983-01-01

    A negative ion source of the type where negative ions are formed by bombarding a low-work-function surface with positive ions and neutral particles from a plasma, wherein a highly ionized plasma is injected into an anode space containing the low-work-function surface. The plasma is formed by hollow cathode discharge and injected into the anode space along the magnetic field lines. Preferably, the negative ion source is of the magnetron type.

  1. Physical effects of negative air ions in a wet sauna

    Microsoft Academic Search

    I. Watanabe; Hiroshi Noro; Yoshinori Ohtsuka; Yukio Mano; Yuko Agishi

    1997-01-01

    The physical effects of negative air ions on humans were determined in an experimental sauna room equipped with an ionizer.\\u000a Thirteen healthy persons took a wet sauna bath (dry bulb temperature 42°?C, relative humidity 100%, 10?min exposure) with\\u000a or without negative air ions. The subjects were not told when they were being exposed to negative air ions. There were no

  2. A surface ionization source 

    E-print Network

    Buzatu, Daniel J.

    1995-01-01

    The main part of the work described herein is the development and testing of a surface ionization source for use on a collinear fast beam laser spectroscopy apparatus. A description of the previously existing fast beam apparatus is given...

  3. Endpoint contribution to the instantaneous ionization rate for tunneling ionization

    NASA Astrophysics Data System (ADS)

    Ivanov, I. A.; Nam, Chang Hee; Kim, Kyung Taec

    2015-06-01

    We examine the instantaneous ionization amplitudes and instantaneous ionization rates for the process of tunneling ionization. We show that the endpoint contribution usually neglected in the asymptotic evaluation of the amplitudes, may be significant. For weak fields the instantaneous ionization rate is largely defined by this contribution. For higher field strengths of the order of 0.1 a.u., the account of this contribution allows one to reproduce numerically computed instantaneous ionization rates with higher accuracy.

  4. Orbital alignment in photodissociation probed using strong field ionization

    SciTech Connect

    Lin Yunfei; Yan Lu; Lee, Suk Kyoung; Herath, Thushani; Li Wen [Department of Chemistry, Wayne State University, Detroit, Michigan 48202 (United States)

    2011-12-21

    The photodissociation of molecules often produces atomic fragments with polarized electronic angular momentum, and the atomic alignment, for example, can provide valuable information on the dynamical pathways of chemical reactions unavailable by other means. In this work, we demonstrate for the first time that orbital polarization in chemical reactions can be measured with great sensitivity using strong field ionization by exploiting its extreme nonlinearity.

  5. Ionizing radiation and its risks.

    PubMed

    Goldman, M

    1982-12-01

    Penetrating ionizing radiation fairly uniformly puts all exposed molecules and cells at approximately equal risk for deleterious consequences. Thus, the original deposition of radiation energy (that is, the dose) is unaltered by metabolic characteristics of cells and tissue, unlike the situation for chemical agents. Intensely ionizing radiations, such as neutrons and alpha particles, are up to ten times more damaging than sparsely ionizing sources such as x-rays or gamma rays for equivalent doses. Furthermore, repair in cells and tissues can ameliorate the consequences of radiation doses delivered at lower rates by up to a factor of ten compared with comparable doses acutely delivered, especially for somatic (carcinogenic) and genetic effects from x- and gamma-irradiation exposure. Studies on irradiated laboratory animals or on people following occupational, medical or accidental exposures point to an average lifetime fatal cancer risk of about 1 x 10(-4) per rem of dose (100 per 10(6) person-rem). Leukemia and lung, breast and thyroid cancer seem more likely than other types of cancer to be produced by radiation. Radiation exposures from natural sources (cosmic rays and terrestrial radioactivity) of about 0.1 rem per year yield a lifetime cancer risk about 0.1 percent of the normally occurring 20 percent risk of cancer death. An increase of about 1 percent per rem in fatal cancer risk, or 200 rem to double the "background" risk rate, is compared with an estimate of about 100 rem to double the genetic risk. Newer data suggest that the risks for low-level radiation are lower than risks estimated from data from high exposures and that the present 5 rem per year limit for workers is adequate. PMID:6761969

  6. Ionizing Radiation and Its Risks

    PubMed Central

    Goldman, Marvin

    1982-01-01

    Penetrating ionizing radiation fairly uniformly puts all exposed molecules and cells at approximately equal risk for deleterious consequences. Thus, the original deposition of radiation energy (that is, the dose) is unaltered by metabolic characteristics of cells and tissue, unlike the situation for chemical agents. Intensely ionizing radiations, such as neutrons and alpha particles, are up to ten times more damaging than sparsely ionizing sources such as x-rays or gamma rays for equivalent doses. Furthermore, repair in cells and tissues can ameliorate the consequences of radiation doses delivered at lower rates by up to a factor of ten compared with comparable doses acutely delivered, especially for somatic (carcinogenic) and genetic effects from x- and gamma-irradiation exposure. Studies on irradiated laboratory animals or on people following occupational, medical or accidental exposures point to an average lifetime fatal cancer risk of about 1 × 10-4 per rem of dose (100 per 106 person-rem). Leukemia and lung, breast and thyroid cancer seem more likely than other types of cancer to be produced by radiation. Radiation exposures from natural sources (cosmic rays and terrestrial radioactivity) of about 0.1 rem per year yield a lifetime cancer risk about 0.1 percent of the normally occurring 20 percent risk of cancer death. An increase of about 1 percent per rem in fatal cancer risk, or 200 rem to double the “background” risk rate, is compared with an estimate of about 100 rem to double the genetic risk. Newer data suggest that the risks for low-level radiation are lower than risks estimated from data from high exposures and that the present 5 rem per year limit for workers is adequate. PMID:6761969

  7. Nonneutral and quasi-neutral diffusion of weakly ionized multiconstituent plasma

    Microsoft Academic Search

    R. J. Hill

    1978-01-01

    A theory is developed for ambipolar diffusion in a multiconstituent weakly ionized plasma. The implications of the presence of negative ions and of differing positive ion and negative ion diffusion coefficients are found. In particular, the presence of numerous negative ions is found to enhance the diffusion of the electrons. Furthermore, this theory of multiconstituent ambipolar diffusion is extended to

  8. Prompt ionization in the CRIT II barium releases. [Critical Ionization Tests

    NASA Technical Reports Server (NTRS)

    Torbert, R. B.; Kletzing, C. A.; Liou, K.; Rau, D.

    1992-01-01

    Observations of electron and ion distributions inside a fast neutral barium jet in the ionosphere show significant fluxes within 4 km of release, presumably related to beam plasma instability processes involved in the Critical Ionization Velocity (CIV) effect. Electron fluxes exceeding 5 x 10 exp 12/sq cm-str-sec-keV were responsible for ionizing both the streaming barium and ambient oxygen. Resulting ion fluxes seem to be consistent with 1-2 percent ionization of the fast barium, as reported by optical observations, although the extended spatial distribution of the optically observed ions is difficult to reconcile with the in situ observations. When the perpendicular velocity of the neutrals falls below critical values, these processes shut off. Although these observations resemble the earlier Porcupine experimental results (Haerendel, 1982), theoretical understanding of the differences between these data and that of earlier negative experiments is still lacking.

  9. Surface ionization of terpene hydrocarbons

    SciTech Connect

    Zandberg, E.Y.; Nezdyurov, A.L.; Paleev, V.I.; Ponomarev, D.A.

    1986-09-01

    By means of a surface ionization indicator for traces of materials in the atmosphere it has been established that many natural materials containing terpenes and their derivatives are ionized on the surface of heated molybdenum oxide at atmospheric air pressure. A mass-spectrometer method has been used to explain the mechanism of ionization of individual terpene hydrocarbons and to establish its principles. The ionization of ..cap alpha..-pinene, alloocimene, camphene, and also adamantane on oxidized tungsten under vacuum conditions has been investigated. The ..cap alpha..-pinene and alloocimene are ionized by surface ionization but camphene and adamantane are not ionized under vacuum conditions. The surface ionization mass spectra of ..cap alpha..-pinene and alloocimene are of low line brightness in comparison with electron ionization mass spectra and differ between themselves. The temperature relations for currents of the same compositions of ions during ionization of ..cap alpha..-pinene and alloocimene are also different, which leads to the possibility of surface ionization analysis of mixtures of terpenes being ionized. The ionization coefficients of alloocimene and ..cap alpha..-pinene on oxidized tungsten under temperatures optimum for ionization and the ionization potentials of alloocimene molecules and of radicals (M-H) of both compounds have been evaluated.

  10. Negative glow discharges for lighting

    SciTech Connect

    Kudryavtsev, A.A.; Lasaryuk, S.N. [Saint-Petersburg Univ. (Russian Federation); Sheverev, V.A. [Polytechnic Univ., Brooklyn, NY (United States)

    1996-12-31

    Results of experimental and theoretical studies of negative glow (NG) discharge devices with original electrode configurations are reported. For the conventional low pressure discharge, the radiation intensity of the negative glow is several times greater than that of the positive column because most of the energy supplied to the NG is converted to excitation and ionization of gas particles. However, applications of NG plasmas have been impaired by the practical difficulty of obtaining extended NG. For laser-pumping, extended negative glow plasmas has been achieved with electrode constructions called hollow cathodes (HC). They can be described as discharge devices in which the cathode surrounds a volume of space, forming a cavity. The anode is placed so that the minimal distance between the cathode and the anode, d, conforms to the condition of hindered discharge. Extended NG plasmas are formed in the space surrounded by the cathode, and no positive column develops. In contrast to various kinds of HC, electrode configurations where an extended NG plasma is formed outside the electrodes are presented. A self-sustained kinetic model of the discharges is developed. Predicted electrical and spectroscopic characteristics of the discharge plasmas are compared with experimental measurements.

  11. Negative thermal ion mass spectrometry of osmium, rhenium, and iridium

    Microsoft Academic Search

    R. A. Creaser; D. A. Papanastassiou; G. J. Wasserburg

    1991-01-01

    The authors report on a technique for obtaining intense ion beams of negatively charged oxides of Os, Re, and Ir by thermal ionization, in a conventional surface ionization mass spectrometer. It was found that the principal ion species of Os, Re, and Ir produced are OsOâ⁻, ReOâ⁻, and IrOâ⁻. The sharp distinction in the masses of the dominant molecular species

  12. Relativistic runaway ionization fronts.

    PubMed

    Luque, A

    2014-01-31

    We investigate the first example of self-consistent impact ionization fronts propagating at relativistic speeds and involving interacting, high-energy electrons. These fronts, which we name relativistic runaway ionization fronts, show remarkable features such as a bulk speed within less than one percent of the speed of light and the stochastic selection of high-energy electrons for further acceleration, which leads to a power-law distribution of particle energies. A simplified model explains this selection in terms of the overrun of Coulomb-scattered electrons. Appearing as the electromagnetic interaction between electrons saturates the exponential growth of a relativistic runaway electron avalanche, relativistic runaway ionization fronts may occur in conjunction with terrestrial gamma-ray flashes and thus explain recent observations of long, power-law tails in the terrestrial gamma-ray flash energy spectrum. PMID:24580462

  13. Relativistic Runaway Ionization Fronts

    NASA Astrophysics Data System (ADS)

    Luque, A.

    2014-01-01

    We investigate the first example of self-consistent impact ionization fronts propagating at relativistic speeds and involving interacting, high-energy electrons. These fronts, which we name relativistic runaway ionization fronts, show remarkable features such as a bulk speed within less than one percent of the speed of light and the stochastic selection of high-energy electrons for further acceleration, which leads to a power-law distribution of particle energies. A simplified model explains this selection in terms of the overrun of Coulomb-scattered electrons. Appearing as the electromagnetic interaction between electrons saturates the exponential growth of a relativistic runaway electron avalanche, relativistic runaway ionization fronts may occur in conjunction with terrestrial gamma-ray flashes and thus explain recent observations of long, power-law tails in the terrestrial gamma-ray flash energy spectrum.

  14. Current status of the application of ionizing radiation to environmental protection: I. Ionizing radiation sources, natural and drinking water purification (A Review)

    Microsoft Academic Search

    A. K. Pikaev

    2000-01-01

    Present-day applications of ionizing radiation to environmental protection are surveyed. This part of the review summarizes\\u000a new data on the ionizing radiation sources used in this area, on the radiation-chemical purification of polluted natural and\\u000a drinking water, and on the mechanisms of processes occurring in these systems under exposure to ionizing radiation. A particular\\u000a emphasis is placed on large-scale processes.

  15. Impact ionization study

    NASA Technical Reports Server (NTRS)

    Whipple, E. C., Jr.

    1982-01-01

    The impact ionization phenomenon which was observed on certain spacecraft was studied. The phenomenon occurs when a neutral atom, molecule, or ion strikes a surface with sufficient kinetic energy that either the incident neutral or atoms on the surface are ionized, with subsequent escape of ions and/or electrons. The released ions and electrons can interfere with measurements on the spacecraft by confusing interpretation of the data. On the other hand, there is the possibility that the effect could be developed into a diagnostic tool for investigating neutral atmospheric species or for studying physical processes on spacecraft surfaces.

  16. High performance liquid chromatography-electrospray ionization-mass spectrometry with programmed ionization mode switching and time segment scanning approach for quantifying multi-components in traditional complex herbal medicines, Qiong-Yu-Gao as an example.

    PubMed

    Xu, Jin-Di; Wu, Jie; Zhou, Shan-Shan; Shen, Hong; Mao, Qian; Zhu, He; Kong, Ming; Li, Song-Lin

    2015-08-10

    An improved high performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS) method was developed to quantitatively evaluate the holistic quality of traditional complex herbal medicines (CHMs). Qiong-Yu-Gao (QYG), a classical CHM consisting of Rehmanniae Radix, Poriae and Ginseng Radix, was used as an example. Thirty-eight major components (including six pairs of epimers/isomers) belonging to five chemical types, i.e., iridoid glycosides, phenethylacohol glycosides, furfural derivatives, ginsenosides and triterpenoid acids, were selected as marker compounds. Programmed ionization mode switching and time segment scanning were designed to improve the sensitivity of the MS detection concerning the diverse chemical features of the analytes. The reference compounds of the analytes were individually injected directly into MS to optimize the ionization cone voltage and to select monitoring ion of each analyte. Nine channels with eight time segments were determined for monitoring the thirty-eight analytes, among which six were detected in positive and thirty-two in negative ion modes respectively. Higher signal-to-noise ratios of the analytes were achieved when compared with full time scanning. In addition, the linearity, precision, accuracy and stability of the method were also validated. The established method was applied for the quantitative evaluation of QYG samples prepared with three different methods. Obvious difference in the contents of thirty-eight components, in particular the original ginsenosides, degraded ginsenosides and furfural derivatives, was found among these QYG samples. All these results demonstrated that the established HPLC-ESI-MS with programmed ionization mode switching and time segment scanning approach is very suitable for the standardization investigation of CHMs. PMID:25982197

  17. Avalanche Ionization and the Limiting Diameter of Filaments Induced by Light Pulses in Transparent Media

    Microsoft Academic Search

    Eli Yablonovitch; N. Bloembergen

    1972-01-01

    A limiting intensity is shown to exist for light propagation in transparent liquids and solids. In pure bulk materials it is determined by avalanche ionization over a wide range of pulse durations, wavelengths, and band gaps. The ionization rate per unit time is deduced from the thickness dependence of the dc breakdown. The negative real part of the index of

  18. Electron impact ionization and attachment cross sections for H2S. [in comet and planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Rao, M. V. V. S.; Srivastava, S. K.

    1993-01-01

    Experiments were performed to measure, by electron impact, appearance potentials and the cross sections for ionization, dissociative ionization, and electron attachment for H2S. Results are presented, and discussed individually, for both positive and negative ions. A schematic diagram of the experimental setup is included.

  19. Ionizing radiation and life.

    PubMed

    Dartnell, Lewis R

    2011-01-01

    Ionizing radiation is a ubiquitous feature of the Cosmos, from exogenous cosmic rays (CR) to the intrinsic mineral radioactivity of a habitable world, and its influences on the emergence and persistence of life are wide-ranging and profound. Much attention has already been focused on the deleterious effects of ionizing radiation on organisms and the complex molecules of life, but ionizing radiation also performs many crucial functions in the generation of habitable planetary environments and the origins of life. This review surveys the role of CR and mineral radioactivity in star formation, generation of biogenic elements, and the synthesis of organic molecules and driving of prebiotic chemistry. Another major theme is the multiple layers of shielding of planetary surfaces from the flux of cosmic radiation and the various effects on a biosphere of violent but rare astrophysical events such as supernovae and gamma-ray bursts. The influences of CR can also be duplicitous, such as limiting the survival of surface life on Mars while potentially supporting a subsurface biosphere in the ocean of Europa. This review highlights the common thread that ionizing radiation forms between the disparate component disciplines of astrobiology. PMID:21774684

  20. Associative ionization in mercury

    SciTech Connect

    Folan, L.M.; Sheverev, V.A. [Polytechnic Univ., Brooklyn, NY (United States). Dept. of Applied Mathematics and Physics

    1996-12-31

    Ionization in binary collisions of 6{sup 3}P{sub 0,1,2} excited mercury atoms are of particular importance for the charge particle balance in low temperature mercury-rare gas plasmas, which have found wide and successful application in fluorescent lamps. The principal weak point of existing theoretical models of lighting plasmas is the choice of processes assumed to lead to ionization in collisions of 6{sup 3}P atoms of mercury, and hence to large uncertainties in the cross-section and rate constant data. In fact, the cross-section values used in discharge models differ by more than a factor of ten. Binary 6{sup 3}P{sub 0} collisions, usually neglected, are expected to be of great importance. The authors preset numerical results from the GLOMAC model, showing the variation in fluorescent lamp operating characteristics as the rate constants for ionization in collisions of 6{sup 3}P atoms are varied through the range allowed by existing experimental results. The notable dependencies observed illustrate the need for more accurate experimental data. A novel experimental approach to the measurement of absolute collisional ionization cross-sections, based on a radio frequency ion trap, is proposed.

  1. IONIZING RADIATION OF EGGS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Contamination of eggs and egg products by Salmonella is associated with a significant number of illnesses in the U.S. each year. Ionizing radiation can inactivate Salmonella on the egg surface, in the egg white, and in the yolk of shell eggs, and has been approved by the U.S. FDA at doses up to 3.0...

  2. Ionization photophysics and spectroscopy of cyanoacetylene

    NASA Astrophysics Data System (ADS)

    Leach, Sydney; Garcia, Gustavo A.; Mahjoub, Ahmed; Bénilan, Yves; Fray, Nicolas; Gazeau, Marie-Claire; Gaie-Levrel, François; Champion, Norbert; Schwell, Martin

    2014-05-01

    Photoionization of cyanoacetylene was studied using synchrotron radiation over the non-dissociative ionization excitation range 11-15.6 eV, with photoelectron-photoion coincidence techniques. The absolute ionization cross-section and spectroscopic aspects of the parent ion were recorded. The adiabatic ionization energy of cyanoacetylene was measured as 11.573 ± 0.010 eV. A detailed analysis of photoelectron spectra of HC3N involves new aspects and new assignments of the vibrational components to excitation of the A2?+ and B2? states of the cation. Some of the structured autoionization features observed in the 11.94 to 15.5 eV region of the total ion yield (TIY) spectrum were assigned to two Rydberg series converging to the B2? state of HC3N+. A number of the measured TIY features are suggested to be vibrational components of Rydberg series converging to the C2?+ state of HC3N+ at ?17.6 eV and others to valence shell transitions of cyanoacetylene in the 11.6-15 eV region. The results of quantum chemical calculations of the cation electronic state geometries, vibrational frequencies and energies, as well as of the C-H dissociation potential energy profiles of the ground and electronic excited states of the ion, are compared with experimental observations. Ionization quantum yields are evaluated and discussed and the problem of adequate calibration of photoionization cross-sections is raised.

  3. ChemTeacher: Ionization Energy

    NSDL National Science Digital Library

    2011-01-01

    ChemTeacher compiles background information, videos, articles, demonstrations, worksheets and activities for high school teachers to use in their classrooms. The Ionization Energy page includes resources for teaching students about trends in ionization energy.

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

    Microsoft Academic Search

    J. Lettry; R. Catherall; U. Köster; U. Georg; O. Jonsson; S. Marzari; V. Fedosseev

    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 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

  5. Removal of organic pollutants by surfactant modified zeolite: comparison between ionizable phenolic compounds and non-ionizable organic compounds.

    PubMed

    Xie, Jie; Meng, Wenna; Wu, Deyi; Zhang, Zhenjia; Kong, Hainan

    2012-09-15

    The aim of this study was to examine the adsorption capability and mechanism of hexadecyltrimethylammonium modified zeolite, which was synthesized from coal fly ash, for the removal of ionizable phenolic compounds (phenol, p-chlorophenol and bisphenol A, with different pK(a)) and non-ionizable organic compounds (aniline, nitrobenzene, and naphthalene, with different hydrophobicity). The obtained zeolite was identified as type Na-P1 (Na(6)Al(6)Si(10)O(32)·12H(2)O, JCPDS code 39-0219), which is classified into the gismondine group with a pore size of 3.1 Å × 4.5 Å [100] and 2.8 Å × 4.8 Å [101]. The adsorption of the two kinds of organic compounds was due to loaded surfactant bilayer because modified zeolite showed great ability for the removal of organic chemicals while little adsorption by zeolite was observed. The isotherm data of ionizable compounds fitted well to the Langmuir model but those of non-ionizable chemicals followed a linear equation. Uptake of ionizable compounds depended greatly on pH, increasing at alkaline pH conditions. In contrary, adsorption of non-ionizable chemicals was essentially the same at all pH levels studied. The adsorption of both kinds of organic compounds correlated well to k(ow) value, suggesting that more hydrophobic organic contaminants are more easily retained by modified zeolite. Based on the different adsorption behavior, the uptake of non-ionizable pollutants was thought to be a single partitioning process into the surfactant bilayer. For ionizable compounds, however, interaction of the phenol group(s) with the positively charged "head" of surfactant additionally functions. PMID:22771348

  6. Negative-ion states

    SciTech Connect

    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.

  7. Negative ion generator

    DOEpatents

    Stinnett, R.W.

    1984-05-08

    A negative ion generator is formed from a magnetically insulated transmission line having a coating of graphite on the cathode for producing negative ions and a plurality of apertures on the opposed anode for the release of negative ions. Magnetic insulation keeps electrons from flowing from the cathode to the anode. A transverse magnetic field removes electrons which do escape through the apertures from the trajectory of the negative ions. 8 figs.

  8. Negative ion generator

    DOEpatents

    Stinnett, Regan W. (Albuquerque, NM)

    1984-01-01

    A negative ion generator is formed from a magnetically insulated transmission line having a coating of graphite on the cathode for producing negative ions and a plurality of apertures on the opposed anode for the release of negative ions. Magnetic insulation keeps electrons from flowing from the cathode to the anode. A transverse magnetic field removes electrons which do escape through the apertures from the trajectory of the negative ions.

  9. Towards energy resolution at the statistical limit from a negative ion time projection chamber

    E-print Network

    Peter Sorensen; Mike Heffner; Adam Bernstein; Josh Renner; Melinda Sweany

    2012-05-29

    We make a proof-of-principle demonstration that improved energy resolution can be obtained in a negative-ion time projection chamber, by individually counting each electron produced by ionizing radiation.

  10. Sentential Negation in English

    ERIC Educational Resources Information Center

    Mowarin, Macaulay

    2009-01-01

    This paper undertakes a detailed analysis of sentential negation in the English language with Chomsky's Government-Binding theory of Transformational Grammar as theoretical model. It distinguishes between constituent and sentential negation in English. The essay identifies the exact position of Negation phrase in an English clause structure. It…

  11. Tevatron ionization profile monitoring

    SciTech Connect

    Jansson, A.; Bowie, K.; Fitzpatrick, T.; Kwarciany, R.; Lundberg, C.; Slimmer, D.; Valerio, L.; Zagel, J.; /Fermilab

    2006-06-01

    Ionization Profile monitors have been used in almost all machines at Fermilab. However, the Tevatron presents some particular challenges with its two counter-rotating, small beams, and stringent vacuum requirements. In order to obtain adequate beam size accuracy with the small signals available, custom made electronics from particle physics experiments was employed. This provides a fast (single bunch) and dead-timeless charge integration with a sensitivity in the femto-Coulomb range, bringing the system close to the single ionization electron detection threshold. The detector itself is based on a previous Main Injector prototype, albeit with many modifications and improvements. The first detector was installed at the end of 2005, and the second detector during the spring shutdown. The ultimate goal is to continuously monitor beam size oscillations at injection, as well as the beam size evolution during ramp and squeeze. Initial results are very encouraging.

  12. The free-free opacity in warm, dense, and weakly ionized helium.

    SciTech Connect

    Kowalski, P. M. (Piotr M.); Mazevet, S. (Stephane); Saumon, D. (Didier)

    2005-01-01

    We investigate the ionization and the opacity of warm, dense helium under conditions found in the atmospheres of cool white dwarf stars. Our particular interest is in densities up to 3 g/cm{sup 3} and temperatures from 1000K to 10000K. For these physical conditions various approaches for modeling the ionization equilibriumpredict ionization fractions that differ by orders of magnitudes. Furthermore, estimates of the density at which helium pressure-ionizes vary from 0.3 to 14 g/cm{sup 3}. In this context, the value of the electron-atom inverse bremsstrahlung absorption is highly uncertain. We present new results obtained from a non-ideal chemical model for the ionization equilibrium, from Quantum Molecular Dynamics (QMD) simulations, and from the analysis of experimental data to better understand the ionization fraction in fluid helium in the weak ionization limit.

  13. Gas-phase Meerwein reaction of epoxides with protonated acetonitrile generated by atmospheric pressure ionizations

    Microsoft Academic Search

    Lianming Wu; David Q. Liu; Alireza S. Kord

    2010-01-01

    Ethylnitrilium ion can be generated by protonation of acetonitrile (when used as the LC-MS mobile phase) under the conditions\\u000a of atmospheric pressure ionizations, including electrospray ionization (ESI) and atmospheric pressure chemical ionization\\u000a (APCI) as well as atmospheric pressure photoionization (APPI). Ethylnitrilium ion ($$CH_3 - C \\\\equiv \\\\mathop N\\\\limits^ + H$$ and its canonical form $$CH_3 - \\\\mathop C\\\\limits^ + =

  14. Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Kelly, Ryan T.; Marginean, Ioan; Tang, Keqi

    2014-06-13

    Electrospray Ionization (ESI) is a process whereby gas phase ions are created from molecules in solution. As a solution exits a narrow tube in the presence of a strong electric field, an aerosol of charged droplets are is formed that produces gas phase ions as they it desolvates. ESI-MS comprises the creation of ions by ESI and the determination of their mass to charge ratio (m/z) by MS.

  15. Hysteresis of ionization waves

    NASA Astrophysics Data System (ADS)

    Dinklage, A.; Bruhn, B.; Testrich, H.; Wilke, C.

    2008-06-01

    A quasi-logistic, nonlinear model for ionization wave modes is introduced. Modes are due to finite size of the discharge and current feedback. The model consists of competing coupled modes and it incorporates spatial wave amplitude saturation. The hysteresis of wave mode transitions under current variation is reproduced. Sidebands are predicted by the model and found in experimental data. The ad hoc model is equivalent to a general—so-called universal—approach from bifurcation theory.

  16. Ionization of Molecular Hydrogen

    NASA Astrophysics Data System (ADS)

    Liu, Xianming; Shemansky, Donald E.

    2004-10-01

    A general model, based on a theoretically calculated ionization oscillator strength and an experimentally determined excitation shape function, has been obtained for calculating the molecular hydrogen electron-impact ionization cross section of a transition between any discrete vibrational levels of the neutral X1?+g state and ionic X2?+g state. Specifically, the excitation shape function and ionization oscillator strength for transitions from the vi=0 level of the X1?+g neutral state to the discrete levels of the X2?+g ionic state are derived from analyzing several experimental measurements. The derived oscillator strength is found to be consistent with the 1994 photoabsorption measurements of Samson & Haddad and the 1977 theoretical cross sections of Flannery and coworkers. The derived excitation function, along with the oscillator strengths for transitions involving the vi>0 level calculated from the data of Flannery and coworkers, permits an accurate calculation of the nondissociative cross sections of H2 between any discrete vibrational levels over a wide energy range.

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

    PubMed Central

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

    2008-01-01

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

  18. Dissociative ionization of biomolecules

    NASA Astrophysics Data System (ADS)

    Huo, Winifred

    2004-09-01

    Dissociative ionization (DI) by electron impact plays a role in many different applications, including low-temperature plasma processing, the study of space and astrophysical plasmas, and the study of biological damages by high-energy radiation. In the present study, our goal is to understand the health hazard to humans from exposure to radiation during an extended space flight. DI by secondary electrons can damage the DNA, either directly by causing a DNA lesion, or indirectly by producing radicals and cations that attack the DNA. The theoretical model employed makes use of the fact that electronic motion is much faster than nuclear motion, allowing DI to be treated as a two-step process. The first step is electron-impact ionization resulting in a dissociative state of the molecular ion with the same geometry as the neutral molecule. In the second step the ion relaxes from the initial geometry and undergoes unimolecular dissociation. Thus the DI cross section is given by the product of the ionization cross section and the dissociation probability. For the ionization process we use the improved binary-encounter dipole (iBED) model. For unimolecular dissociation, we use the multiconfigurational self-consistent field (MCSCF) method to determine the minimum energy pathways to possible product channels. This model has been applied to study the DI of H_2O, NH_3, and CH_4, and the results are in good agreement with experiment. The DI from the low-lying channels of benzene has also been studied and the dissociation products are compared with photoionization measurements. The DI of the DNA bases guanine and cytosine are then discussed. Of the four DNA bases, guanine has the largest ionization cross section and cytosine has the smallest. The guanine radical cation is considered to be one of the precursors to the primary, direct-type lesions formed in DNA when it is irradiated. Comparison of DI products of guanine and cytosine will be made to understand the differences in their behavior upon irradiation.

  19. Long-time joint spectra and entanglement of two photoelectrons originating in interacting auto-ionization systems

    NASA Astrophysics Data System (ADS)

    Pe?ina, Jan, Jr.; Lukš, Antonín; Leo?ski, Wieslaw

    2015-06-01

    Two auto-ionization systems in a stationary optical field that are mutually interacting via the dipole–dipole interaction are considered. Their evolution is found analytically. Joint spectra of two ionized electrons are analyzed in detail in the long-time limit for comparable strengths of direct and indirect ionization paths as well as the dominating indirect ionization path. Entanglement in the state of two ionized electrons is quantified using the density of quadratic negativity. Suitable conditions for obtaining highly entangled states are discussed.

  20. Atmospheric-pressure Penning ionization mass spectrometry.

    PubMed

    Hiraoka, Kenzo; Fujimaki, Susumu; Kambara, Shizuka; Furuya, Hiroko; Okazaki, Shigemitsu

    2004-01-01

    A preliminary study on the atmospheric-pressure Penning ionization (APP(e)I) of gaseous organic compounds with Ar* has been made. The metastable argon atoms (Ar*: 11.55 eV for (3)P(2) and 11.72 eV for (3)P(0)) were generated by the negative-mode corona discharge of atmospheric-pressure argon gas. By applying a high positive voltage (+500 to +1000 V) to the stainless steel capillary for the sample introduction (0.1 mm i.d., 0.3 mm o.d.), strong ion signals could be obtained. The ions formed were sampled through an orifice into the vacuum and mass-analyzed by an orthogonal time-of-flight mass spectrometer. The major ions formed by APP(e)I are found to be molecular-related ions for alkanes, aromatics, and oxygen-containing compounds. Because only the molecules with ionization energies less than the internal energy of Ar* are ionized, the present method will be a selective and highly sensitive interface for gas chromatography/mass spectrometry. PMID:15384154

  1. Liquid chromatography\\/atmospheric pressure ionization-mass spectrometry in drug metabolism studies

    Microsoft Academic Search

    R. Kostiainen; T. Kotiaho; T. Kuuranne; S. Auriola

    2003-01-01

    Thestudyofthemetabolicfateofdrugs isanessentialand importantpartofthedrug developmentprocess. The analysis of metabolites is a challenging task and several different analytical methods have been used in these studies. However, after the introduction of the atmospheric pressure ionization (API) technique, electrospray and atmospheric pressure chemical ionization, liquid chromatography\\/mass spectrometry (LC\\/MS) has become an important and widely used method in the analysis of metabolites owing to its

  2. Electrospray ionization mass spectrometry characterization of musts and alembic brazilian cachaças using selected yeast strains.

    PubMed

    Badotti, Fernanda; Gomes, Fátima C O; Teodoro, Mariana M G; Silva, Alisson Luiz Diniz; Rosa, Carlos Augusto; Machado, Ana Maria de R

    2014-04-01

    The choice of fermentation system during cachaça production can greatly influence the chemical composition of the beverage. In this work, Saccharomyces cerevisiae strains were selected based on fermentative properties and used as starters to produce alembic cachaça. In distillery scale production, the selected yeast strains exhibited greater adaptiblity to the fermentation environment and hence remained predominant throughout the process. Electrospray ionization mass spectrometry in the negative ion mode revealed that most of the compounds present in the must are different from those formed in the distillate for both cachaças obtained from spontaneous and selected strains. However, beverages produced using selected strains showed greater similarity in chemical profiles than those produced from spontaneous strain fermentation. Moreover, a smaller number of ions were detected in beverages produced by selected strain than from spontaneous strain fermentation. Our results indicate that the selected S. cerevisiae strains evaluated are able to produce cachaças less subject to variation in chemical composition. This could potentially improve brand consistency and thus commercial viability, particularly in the international market. PMID:24712492

  3. Electrode activation in cesium-free negative ion sources

    SciTech Connect

    Dudnikov, Vadim; Johnson, Rolland P. [Muons, Inc., Batavia, Illinois 60510 (United States)

    2010-02-15

    Features of emission electrode activation leading to enhancement of negative ion emission in cesium-free discharges are discussed. In some ion sources with cesium-free discharges, the emission of negative ions has been increased significantly by emission electrode activation using strong heating of the negative biased electrode by discharge plasma. A simple explanation of this enhancement is that it is due to an accumulation on the emission surface of the plasma electrode of impurities with low ionization potential that decreases in surface work function and increases the secondary emission of negative ions similar to ''Cesiation.'' The negative biasing of emission surface is important for accumulation and trapping the impurities on the emission surface. To effectively control the activation process it is important to directly detect the evolution of the work function and the impurity concentration during electrode activation with enhancement of negative ion emission.

  4. Negative-ion formation in the explosives RDX, PETN, and TNT using the Reversal Electron Attachment Detection (READ) technique

    NASA Technical Reports Server (NTRS)

    Chutijian, Ara; Boumsellek, S.; Alajajian, S. H.

    1992-01-01

    In the search for high sensitivity and direct atmospheric sampling of trace species, techniques have been developed such as atmospheric-sampling, glow-discharge ionization (ASGDI), corona discharge, atmospheric pressure ionization (API), electron-capture detection (ECD), and negative-ion chemical ionization (NICI) that are capable of detecting parts-per-billion to parts-per-trillion concentrations of trace species. These techniques are based on positive- or negative-ion formation via charge-transfer to the target, or electron capture under multiple-collision conditions in a Maxwellian distribution of electron energies at the source temperature. One drawback of the high-pressure, corona- or glow-discharge devices is that they are susceptible to interferences either through indistinguishable product masses, or through undesired ion-molecule reactions. The ASGDI technique is relatively immune from such interferences, since at target concentrations of less than 1 ppm the majority of negative ions arises via electron capture rather than through ion-molecule chemistry. A drawback of the conventional ECD, and possibly of the ASGDI, is that they exhibit vanishingly small densities of electrons with energies in the range 0-10 millielectron volts (meV), as can be seen from a typical Maxwellian electron energy distribution function at T = 300 K. Slowing the electrons to these subthermal (less than 10 meV) energies is crucial, since the cross section for attachment of several large classes of molecules is known to increase to values larger than 10(exp -12) sq cm at near-zero electron energies. In the limit of zero energy these cross sections are predicted to diverge as epsilon(exp -1/2), where epsilon is the electron energy. In order to provide a better 'match' between the electron energy distribution function and attachment cross section, a new concept of attachment in an electrostatic mirror was developed. In this scheme, electrons are brought to a momentary halt by reversing their direction with electrostatic fields. At this turning point the electrons have zero or near-zero energy. A beam of target molecules is introduced, and the resultant negative ions extracted. This basic idea has been recently improved to allow for better reversal geometry, higher electron currents, lower backgrounds, and increased negative-ion extraction efficiency. We present herein application of the so-called reversal electron attachment detector (READ) to the study of negative-ion formation in the explosives molecules RDX, PETN, and TNT under single-collision conditions.

  5. Negative-ion implantation

    SciTech Connect

    Ishikawa, Junzo [Kyoto Univ., Yoshida, Kyoto (Japan). Dept. of Electronics

    1995-12-31

    Negative-ion implantation is a promising technique for forthcoming ULSI (more than 256 M bits) fabrication and TFT (for color LCD) fabrication, since the surface charging voltage of insulated electrodes or insulators implanted by negative ions is found to saturate within so few as several volts, no breakdown of insulators would be expected without a charge neutralizer in these fabrication processes. Scatter-less negative-ion implantation into powders is also possible. For this purpose an rf-plasma-sputter type heavy negative-ion source was developed, which can deliver several milliamperes of various kinds of negative ion currents such as boron, phosphor, silicon, carbon, copper, oxygen, etc. A medium current negative-ion implanter with a small version of this type of ion source has been developed.

  6. Ionization and Excitation in Non-Polar Organic Liquids.

    ERIC Educational Resources Information Center

    Lipsky, Sanford

    1981-01-01

    Reviews recent advances in radiation chemistry concerning the effect of high-energy radiation on organic liquids. Discusses the general nature of excited and ionized states, pathways for decay, the effect of environmental perturbation, the behavior of an electron in a nonpolar liquid, and comparison of photochemical and radiation chemical effects.…

  7. Effects of ionizing radiation in ginkgo and guarana [rapid communication

    Microsoft Academic Search

    Renata Rabelo Soriani; Lucilia Cristina Satomi; Terezinha De Jesus A. Pinto

    2005-01-01

    Raw plant materials normally carry high bioburden due to their origin, offering potential hazards to consumers. The use of decontamination processes is therefore an important step towards the consumer safety and therapeutical efficiency. Several authors have reported the treatment of medicinal herbs with ionizing radiation. This work evaluated the effects of different radiation doses on the microbial burden and chemical

  8. Effects of ionizing radiation in ginkgo and guarana

    Microsoft Academic Search

    Renata Rabelo Soriani; Lucilia Cristina Satomi; Terezinha de Jesus A. Pinto

    2005-01-01

    Raw plant materials normally carry high bioburden due to their origin, offering potential hazards to consumers. The use of decontamination processes is therefore an important step towards the consumer safety and therapeutical efficiency. Several authors have reported the treatment of medicinal herbs with ionizing radiation. This work evaluated the effects of different radiation doses on the microbial burden and chemical

  9. Negative thermal expansion materials

    Microsoft Academic Search

    J. S. O. Evans; T. A. Mary; A. W. Sleight

    1998-01-01

    The recent discovery of negative thermal expansion over an unprecedented temperature range in ZrW2O8 (which contracts continuously on warming from below 2 K to above 1000 K) has stimulated considerable interest in this unusual phenomenon. Negative and low thermal expansion materials have a number of important potential uses in ceramic, optical and electronic applications. We have now found negative thermal

  10. Negative thermal expansion materials

    Microsoft Academic Search

    J. S. O Evans; T. A Mary; A. W Sleight

    1997-01-01

    The recent discovery of negative thermal expansion over an unprecedented temperature range in ZrW2O8 (which contracts continuously on warming from below 2 K to above 1000 K) has stimulated considerable interest in this unusual phenomenon. Negative and low thermal expansion materials have a number of important potential uses in ceramic, optical and electronic applications. We have now found negative thermal

  11. Negative Ion Density Fronts

    SciTech Connect

    Igor Kaganovich

    2000-12-18

    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.

  12. Negative ions in comets

    NASA Technical Reports Server (NTRS)

    Wekhof, A.

    1981-01-01

    Negative ion sources in comets are identified and cometary plasma effects caused by negative ions are examined. The primary negative ion sources are shown to be: (1) for the inner coma - photodissociation of HCN, electron attachment of OH, and collision with alkalis; (2) in the vicinity of the nucleus - interplanetary dust collisions with the nucleus; and (3) for both the contaminated solar wind region and sporadic discharges in the nonhomogeneous inner coma plasma - dissociative electron attachment and charge inversion during keV positive ion scattering by cometary dust. Negative ion abundance for Halley's Comet has been estimated to be 10 to the -6th - 10 to the -10th of electron densities.

  13. New ionization methods and miniature mass spectrometers for biomedicine: DESI imaging for cancer diagnostics and paper spray ionization for therapeutic drug monitoring.

    PubMed

    Cooks, R Graham; Manicke, Nicholas E; Dill, Allison L; Ifa, Demian R; Eberlin, Livia S; Costa, Anthony B; Wang, He; Huang, Guangming; Ouyang, Zheng

    2011-01-01

    The state-of-the-art in two new ambient ionization methods for mass spectrometry, desorption electrospray ionization (DESI) and paper spray (PS), is described and their utility is illustrated with new studies on tissue imaging and biofluid analysis. DESI is an ambient ionization method that can be performed on untreated histological sections of biological tissue in the open lab environment to image lipids, fatty acids, hormones and other compounds. Paper spray is performed in the open lab too; it involves electrospraying dry blood spots or biofluid deposits from a porous medium. PS is characterized by extreme simplicity and speed: a spot of whole blood or other biofluid is analyzed directly from paper, simply by applying a high voltage to the moist paper. Both methods are being developed for use in diagnostics as a means to inform therapy. DESI imaging is applied to create molecular maps of tissue sections without prior labeling or other sample preparation. Like other methods of mass spectrometry imaging (MSI), it combines the chemical speciation of multiple analytes with information on spatial distributions. DESI imaging provides valuable information which correlates with the disease state of tissue as determined by standard histochemical methods. Positive-ion data are presented which complement previously reported negative-ion data on paired human bladder cancerous and adjacent normal tissue sections from 20 patients. These data add to the evidence already in the literature demonstrating that differences in the distributions of particular lipids contain disease-diagnostic information. Multivariate statistical analysis using principal component analysis (PCA) is used to analyze the imaging MS data, and so confirm differences between the lipid profiles of diseased and healthy tissue types. As more such data is acquired, DESI imaging has the potential to be a diagnostic tool for future cancer detection in situ; this suggests a potential role in guiding therapy in parallel with standard histochemical and immunohistological methods. The PS methodology is aimed at high-throughput clinical measurement of quantitative levels of particular therapeutic agents in blood and other biofluids. The experiment allows individual drugs to be quantified at therapeutic levels and data is presented showing quantitative drug analysis from mixtures of therapeutic drugs in whole blood. Data on cholesterol sulfate, a new possible prostate biomarker seen at elevated levels in diseased prostate tissue, but not in healthy prostate tissue in serum are reported using paper spray ionization. PMID:21413184

  14. Influence of air humidity and the distance from the source on negative air ion concentration in indoor air

    Microsoft Academic Search

    Chih Cheng Wu; Grace W. M. Lee; Shinhao Yang; Kuo-Pin Yu; Chia Ling Lou

    2006-01-01

    Although negative air ionizer is commonly used for indoor air cleaning, few studies examine the concentration gradient of negative air ion (NAI) in indoor environments. This study investigated the concentration gradient of NAI at various relative humidities and distances form the source in indoor air. The NAI was generated by single-electrode negative electric discharge; the discharge was kept at dark

  15. High Pressure (>1 atm) Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

    2011-03-01

    High pressure electrospray ionization mass spectrometry has been performed by pressurizing a custom made ion source chamber with compressed air to a pressure higher than the atmospheric pressure. The ion source was coupled to a commercial time-of-flight mass spectrometer using a nozzle-skimmer arrangement. The onset voltage for the electrospray of aqueous solution was found to be independent on the operating pressure. The onset voltage for the corona discharge, however, increased with the rise of pressure following the Paschen's law. Thus, besides having more working gas for the desolvation process, gaseous breakdown could also be avoided by pressurizing the ESI ion source with air to an appropriate level. Stable electrospray ionization has been achieved for the sample solution with high surface tension such as pure water in both positive and negative ion modes. Fragmentation of labile compounds during the ionization process could also be reduced by optimizing the operating pressure of the ion source.

  16. Prompt ionization in the CRIT II barium releases

    NASA Astrophysics Data System (ADS)

    Torbert, R. B.; Kletzing, C. A.; Liou, K.; Rau, D.

    1992-05-01

    Observations of electron and ion distributions inside a fast neutral barium jet in the ionosphere show significant fluxes within 4 km of release, presumably related to beam plasma instability processes involved in the Critical Ionization Velocity (CIV) effect. Electron fluxes exceeding 5 x 10 exp 12/sq cm-str-sec-keV were responsible for ionizing both the streaming barium and ambient oxygen. Resulting ion fluxes seem to be consistent with 1-2 percent ionization of the fast barium, as reported by optical observations, although the extended spatial distribution of the optically observed ions is difficult to reconcile with the in situ observations. When the perpendicular velocity of the neutrals falls below critical values, these processes shut off. Although these observations resemble the earlier Porcupine experimental results (Haerendel, 1982), theoretical understanding of the differences between these data and that of earlier negative experiments is still lacking.

  17. Rapid and simultaneous determination of sulfonate ester genotoxic impurities in drug substance by liquid chromatography coupled to tandem mass spectrometry: comparison of different ionization modes.

    PubMed

    Guo, Tian; Shi, Yuanyuan; Zheng, Li; Feng, Feng; Zheng, Feng; Liu, Wenyuan

    2014-08-15

    Two ionization techniques for liquid chromatography-mass spectrometry (LC-MS) determination of sulfonate ester potentially genotoxic impurities (PGIs) were evaluated. Twelve PGIs including methyl, ethyl, propyl and isopropyl esters of methanesulfonate, benzenesulfonate and p-toluenesulfonate were studied in this research. Electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) sources were compared in terms of performance and quality parameters for detection of the twelve PGIs. Their mass spectra obtained by APCI and ESI were very different in both fragment ions and relative abundances. In APCI negative ion mode the twelve sulfonate esters showed their stable precursor ions of [M-alkyl](-), which readily yielded product ions of [M-alkyl-CH3](-) (for aliphatic sulfonate esters) or [M-alkyl-SO2](-) (for aromatic sulfonate esters) with collision-induced dissociation (CID) applied; and working in selected reaction monitoring (SRM) mode has allowed limits of detection to be decreased. In the case of ESI ionization, these compounds showed their precursor ions [M+H](+), but their abundance was easily competed by formation of ions [M+NH4](+) and/or [M+Na](+), which led to poor analytical sensitivity and reproducibility. Although mobile phase additives could enhance the responses of adduct ions like [M+NH4](+) and [M+Na](+), no improvement was obtained when using SRM mode. Twelve sulfonate esters were systematically compared and APCI was shown to be a better ionization technique for rapid and sensitive determination of these PGIs. Performance of the developed approach for rapid determination of 12 PGIs was also evaluated. Quality parameters were established and good precision (relative standard deviations <8%) and very low limits (2-4ng/mL) of detection were obtained, mainly when using APCI in SRM mode. PMID:24997109

  18. Removal of bioaerosols by the combination of a photocatalytic filter and negative air ions

    Microsoft Academic Search

    Kuo-Pin Yu; Grace Whei-May Lee; Szu-Ying Lin; Chien Ping Huang

    2008-01-01

    This study focused on the investigation of the effectiveness of negative air ionization (NAI), photocatalytic oxidation (PCO), and the combination of NAI and PCO on the removal of aerosolized Escherichia coli, Candida famata, and ? vir phage under different relative humidity. The experiments were conducted with a stainless steel reactor equipped with a negative air ion generator, a photocatalytic filter,

  19. Modified calutron negative ion source operation and future plans

    SciTech Connect

    Dagenhart, W.K.; Stirling, W.L.; Haselton, H.H.; Kelley, G.G.; Kim, J.; Tsai, C.C.; Whealton, J.H.

    1980-01-01

    Negative ion generation has advanced rapidly by employing the concept of surface ionization. The modified calutron has proven to be a successful tool to explore these concepts and provide solutions to the many problems which must be evaluated. Many features of the SITEX (Surface Ionization with Transverse Extraction) ion source are ideally suited to this exploration. Some of these features are; a ribbon-like plasma, electron control by transverse magnetic fields and the ability to separate the Cs oven parameters from those which control the positive ion generation.

  20. Magnetic negative stiffness dampers

    NASA Astrophysics Data System (ADS)

    Shi, Xiang; Zhu, Songye

    2015-07-01

    This communication presents the design principle and experimental validation of two novel configurations of magnetic negative stiffness dampers (MNSDs), both of which are composed of several permanent magnets arranged in a conductive pipe. The MNSD, as a passive device, efficiently integrates negative stiffness and eddy-current damping in a simple and compact design, in which the negative stiffness behavior depends on the different arrangements of the permanent magnets. When applied to structural vibration control, passive MNSD may achieve a performance comparable with semi-active or active control in some applications. Laboratory experiments of small-scale prototypes successfully verified the proposed MNSD design concept.

  1. Introduction to Negative Numbers

    NSDL National Science Digital Library

    WNET.org

    2006-01-01

    This lesson plan based on a Cyberchase activity, first addresses a common misconception: starting measurement from 1 instead of 0. Then, it introduces negative numbers by extending a number line beyond 0 in the negative (left) direction. It is motivated by the Cyber Squad’s mission to find the captured Cyberchase Council on a particular floor of a tall building as seen in two quicktime videos: “Importance of the Origin" and "Inventing Negative Numbers" (each are cataloged separately). In addition to the learning activity, other support materials are included: handouts, assessments and answer keys.

  2. Negative birefringent polyimide films

    NASA Technical Reports Server (NTRS)

    Harris, Frank W. (Inventor); Cheng, Stephen Z. D. (Inventor)

    1994-01-01

    A negative birefringent film, useful in liquid crystal displays, and a method for controlling the negative birefringence of a polyimide film is disclosed which allows the matching of an application to a targeted amount of birefringence by controlling the degree of in-plane orientation of the polyimide by the selection of functional groups within both the diamine and dianhydride segments of the polyimide which affect the polyimide backbone chain rigidity, linearity, and symmetry. The higher the rigidity, linearity and symmetry of the polyimide backbone, the larger the value of the negative birefringence of the polyimide film.

  3. Higher-Sensitivity Ionization Trace-Species Detector

    NASA Technical Reports Server (NTRS)

    Boumsellek, Said; Chutjian, Ara

    1995-01-01

    Electron source and electron optics of reversal electron-attachment detector modified to increase sensitivity. Original version described in "High-Sensitivity Ionization Trace-Species Detector" (NPO-17596). Used to detect molecules of particular chemical species of interest (e.g., narcotics, explosives, or organic wastes) present in air at low concentrations, and known to attach extremely low-energy electrons. Apparatus does this by ionizing molecules from sampled atmosphere, then detecting ions of species of interest. Detector features indirectly heated spherical cathode and redesigned electron optics, together, deliver more electrons at low kinetic energy to reversal plane, R. Greater electron current generates more ions for detection.

  4. Zero Volt Paper Spray Ionization and Its Mechanism.

    PubMed

    Wleklinski, Michael; Li, Yafeng; Bag, Soumabha; Sarkar, Depanjan; Narayanan, Rahul; Pradeep, T; Cooks, R Graham

    2015-07-01

    The analytical performance and a suggested mechanism for zero volt paper spray using chromatography paper are presented. A spray is generated by the action of the pneumatic force of the mass spectrometer (MS) vacuum at the inlet. Positive and negative ion signals are observed, and comparisons are made with standard kV paper spray (PS) ionization and nanoelectrospray ionization (nESI). While the range of analytes to which zero volt PS is applicable is very similar to kV PS and nESI, differences in the mass spectra of mixtures are interpreted in terms of the more significant effects of analyte surface activity in the gentler zero volt experiment than in the other methods due to the significantly lower charge. The signal intensity of zero volt PS is also lower than in the other methods. A Monte Carlo simulation based on statistical fluctuation of positive and negative ions in solution has been implemented to explain the production of ions from initially uncharged droplets. Uncharged droplets first break up due to aerodynamics forces until they are in the 2-4 ?m size range and then undergo Coulombic fission. A model involving statistical charge fluctuations in both phases predicts detection limits similar to those observed experimentally and explains the effects of binary mixture components on relative ionization efficiencies. The proposed mechanism may also play a role in ionization by other voltage-free methods. PMID:26024306

  5. Electron-impact ionization and dissociative ionization of biomolecules

    NASA Astrophysics Data System (ADS)

    Huo, Winifred

    2006-05-01

    Oxidative damages by ionizing radiation are the source of radiation-induced damages to human health. It is recognized that secondary electrons play a role in the damage process, particularly important is the damage of DNA by electrons, potentially leading to mutagenesis. The damage can be direct, by creating a DNA lesion, or indirect, by producing radicals that attack the DNA. Molecular-level study of electron interaction with DNA provides information on the damage pathways and dominant mechanisms. This investigation focuses on ionization and dissociative ionization (DI) of DNA fragments by electron-impact. For ionization we use the improved binary-encounter dipole (iBED) model [W.M. Huo, Phys. Rev. A64, 042719-1 (2001)]. For DI it is assumed that electron motion is much faster than nuclear motion, allowing DI to be treated as a two-step process and the DI cross section given by the product of the ionization cross section and dissociation probability. The ionization study covers DNA bases, sugar phosphate backbone, and nucleotides. An additivity principle is observed. For example, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3'- and C5'-deoxyribose-phospate cross sections, differing by less than 5%. The result implies that certain properties of the DNA, like the total ionization cross section, are localized properties and an additivity principle may apply. This allows us to obtain properties of a larger molecular system built up from the results of smaller subsystem fragments. The DI of guanine and cytosine has been studied. For guanine, a proton is produced from the channel where the ionized electron originates from a molecular orbital with significant charge density along the N(1)-H bond. The interaction of the proton with cytosine was also studied.

  6. Positivity, negativity, and entanglement

    E-print Network

    Perlmutter, Eric; Rota, Massimiliano

    2015-01-01

    We explore properties of the universal terms in the entanglement entropy and logarithmic negativity in 4d CFTs, aiming to clarify the ways in which they behave like the analogous entanglement measures in quantum mechanics. We show that, unlike entanglement entropy in finite-dimensional systems, the sign of the universal part of entanglement entropy is indeterminate. In particular, if and only if the central charges obey $a>c$, the entanglement across certain classes of entangling surfaces can become arbitrarily negative, depending on the geometry and topology of the surface. The negative contribution is proportional to the product of $a-c$ and the genus of the surface. Similarly, we show that in $a>c$ theories, the logarithmic negativity does not always exceed the entanglement entropy.

  7. Gram-Negative Bacteria

    Microsoft Academic Search

    Craig A. Martin

    \\u000a Gram-negative bacteria are responsible for a broad array of infections in both the ambulatory and hospital settings. Urinary\\u000a tract infections, otitis media, pneumonia, abdominal infections, and meningitis are among the common and serious diseases\\u000a caused by these pathogens. Beta-lactams including penicillins, cephalosporins, monobactams, and carbapenems, along with fluoroquinolones\\u000a and aminoglycosides, comprise the most commonly used treatment regimens for gram-negative infections.

  8. No to negative data

    SciTech Connect

    Wiley, H. S.

    2008-04-01

    A frequent criticism in biology is that we don’t publish our negative data. As a result, the literature has become biased towards papers that favor specific hypotheses1. Some scientists have become so concerned about this trend that they have created journals dedicated to publishing negative results (e.g. the Journal of Negative Results in Biomedicine). Personally, I don’t think they should bother. I say this because I believe negative results are not worth publishing. Rest assured that I do not include drug studies that show a lack of effectiveness towards a specific disease or condition. This type of finding is significant in a societal context, not a scientific one, and thus we all have a vested interest in seeing this type of result published. I am talking about a set of experimental results that fail to support a particular hypothesis. The problem with these types of negative results is that they don’t actually advance science. Science is a set of ideas that can be supported by observations. A negative result does not support any specific idea, but only tells you what isn’t right. Well, there are only a small number of potential hypotheses that are correct, but essentially an infinite number of ideas are not correct. I don’t want to waste my time reading a paper about what doesn’t happen, just about those things that do. I can remember a positive result because I can associate it with a specific concept. What do I do with a negative one? It is hard enough to following the current literature. A flood of negative results would make that task all but impossible

  9. Pure ionization cross section of helium and ionization mechanism

    NASA Astrophysics Data System (ADS)

    Chen, X. M.; Lu, Y. X.; Gao, Z. M.; Cui, Y.; Liu, Y. W.; Du, J.

    2007-09-01

    Pure target ionization was investigated for 0.4-6.4 MeV C q+ ( q = 1-4) + He and O q+ ( q = 1-4) + He collisions. The double-to-single target ionization ratios R21 were measured using coincidence techniques. We compare our results with existing experimental results and find they are in good agreement. The ratio R21 is nearly independent of projectile charge state. The relation of R21 ˜ V is analyzed using the over barrier model (OBM) and ionization probability, which is described in our extended over barrier model. Our calculation agrees well with the experimental results.

  10. Ionizing gas breakdown waves in strong electric fields.

    NASA Technical Reports Server (NTRS)

    Klingbeil, R.; Tidman, D. A.; Fernsler, R. F.

    1972-01-01

    A previous analysis by Albright and Tidman (1972) of the structure of an ionizing potential wave driven through a dense gas by a strong electric field is extended to include atomic structure details of the background atoms and radiative effects, especially, photoionization. It is found that photoionization plays an important role in avalanche propagation. Velocities, electron densities, and temperatures are presented as a function of electric field for both negative and positive breakdown waves in nitrogen.

  11. Surface effects and electrochemical cell capacitance in desorption electrospray ionization.

    PubMed

    Volný, Michael; Venter, Andre; Smith, Scott A; Pazzi, Marco; Cooks, R Graham

    2008-04-01

    Time resolved measurements show that during a desorption electrospray ionization (DESI) experiment, the current initially rises sharply, followed by an exponential decrease to a relatively steady current. When the high voltage on the spray emitter is switched off, the current drops to negative values, suggesting that the direction of current flow in the equivalent DESI circuit is reversed. These data demonstrate that the DESI source behaves as a dc capacitor and that the addition of a surface between the sprayer and the counter electrode in DESI introduces a new electrically active element into the system. The charging and discharging behavior was observed using different surfaces and it could be seen both by making current measurements on a plate at the entrance to the mass spectrometer as well as by measuring ion current in the linear ion trap within the vacuum system of the mass spectrometer. The magnitude of the steady state current obtained without analyte present on the surface is different for different surface materials, and different capacitor time constants of the equivalent RC circuits were calculated for different DESI surfaces. The PTFE surface has by far the greatest time constant and is also able to produce the highest DESI currents. Surface properties play a crucial role in charge transfer during DESI in addition to the effects of the chemical properties of the analyte. It is suggested that surface energy (wettability) is an important factor controlling droplet behavior on the surface. The experimental data are correlated with critical surface tension values of different materials. It is proposed, based on the results presented, that super-hydrophobic materials with extremely high contact angles have the potential to be excellent DESI substrates. It is also demonstrated, using the example of the neurotransmitter dopamine, that the surface charge that develops during a DESI-MS experiment can cause electrochemical oxidation of the analyte. PMID:18365123

  12. Ionizing radiation promotes protozoan reproduction

    SciTech Connect

    Luckey, T.D.

    1986-11-01

    This experiment was performed to determine whether ionizing radiation is essential for maximum growth rate in a ciliated protozoan. When extraneous ionizing radiation was reduced to 0.15 mrad/day, the reproduction rate of Tetrahymena pyriformis was significantly less (P less than 0.01) than it was at near ambient levels, 0.5 or 1.8 mrad/day. Significantly higher growth rates (P less than 0.01) were obtained when chronic radiation was increased. The data suggest that ionizing radiation is essential for optimum reproduction rate in this organism.

  13. Microwave reflectometer ionization sensor

    NASA Technical Reports Server (NTRS)

    Seals, Joseph; Fordham, Jeffrey A.; Pauley, Robert G.; Simonutti, Mario D.

    1993-01-01

    The development of the Microwave Reflectometer Ionization Sensor (MRIS) Instrument for use on the Aeroassist Flight Experiment (AFE) spacecraft is described. The instrument contract was terminated, due to cancellation of the AFE program, subsequent to testing of an engineering development model. The MRIS, a four-frequency reflectometer, was designed for the detection and location of critical electron density levels in spacecraft reentry plasmas. The instrument would sample the relative magnitude and phase of reflected signals at discrete frequency steps across 4 GHz bandwidths centered at four frequencies: 20, 44, 95, and 140 GHz. The sampled data would be stored for later processing to calculate the distance from the spacecraft surface to the critical electron densities versus time. Four stepped PM CW transmitter receivers were located behind the thermal protection system of the spacecraft with horn antennas radiating and receiving through an insulating tile. Techniques were developed to deal with interference, including multiple reflections and resonance effects, resulting from the antenna configuration and operating environment.

  14. Negative energy waves

    NASA Astrophysics Data System (ADS)

    Lashmore-Davies, C. N.

    2005-04-01

    A brief history of the concept of negative energy waves in fluid and plasma media is given. The theory of microwave tubes is highlighted, where the small signal power theorem was first derived, which led to the interpretation of these devices in terms of the interaction of positive and negative energy waves. Three examples are described to illustrate the use of negative waves in stability problems. The first is concerned with the Kelvin-Helmholtz instability in neutral fluids. The second comes from a kinetic theory of instability in a collisionless shock wave in a magnetized plasma, and the third is concerned with the effect of a resistive wall and plasma flow on the magnetohydrodynamic stability of a magnetically confined plasma. The paper ends with some general conclusions.

  15. Field ionization from carbon nanofibers

    E-print Network

    Adeoti, Bosun J

    2008-01-01

    The Micro Gas Analyzer project aims to develop power-efficient, high resolution, high sensitivity, portable and real-time gas sensors. We developed a field ionizer array based on gated CNTs. Arrays of CNTs are used because ...

  16. Electrospray Ionization-Induced Protein Unfolding

    NASA Astrophysics Data System (ADS)

    Lin, Hong; Kitova, Elena N.; Johnson, Margaret A.; Eugenio, Luiz; Ng, Kenneth K. S.; Klassen, John S.

    2012-12-01

    Electrospray ionization mass spectrometry (ESI-MS) measurements were performed under a variety of solution conditions on a highly acidic sub-fragment (B3C) of the C-terminal carbohydrate-binding repeat region of Clostridium difficile toxin B, and two mutants (B4A and B4B) containing fewer acidic residues. ESI-MS measurements performed in negative ion mode on aqueous ammonium acetate solutions of B3C at low ionic strength ( I < 80 mM) revealed evidence, based on the measured charge state distribution, of protein unfolding. In contrast, no evidence of unfolding was detected from ESI-MS measurements made in positive ion mode at low I or in either mode at higher I. The results of proton nuclear magnetic resonance and circular dichroism spectroscopy measurements and gel filtration chromatography performed on solutions of B3C under low and high I conditions suggest that the protein exists predominantly in a folded state in neutral aqueous solutions with I > 10 mM. The results of ESI-MS measurements performed on B3C in a series of solutions with high I at pH 5 to 9 rule out the possibility that the structural changes are related to ESI-induced changes in pH. It is proposed that unfolding of B3C, observed in negative mode for solutions with low I, occurs during the ESI process and arises due to Coulombic repulsion between the negatively charged residues and liquid/droplet surface charge. ESI-MS measurements performed in negative ion mode on B4A and B4B also reveal a shift to higher charge states at low I but the magnitude of the changes are smaller than observed for B3C.

  17. Ionizing radiation enhances malignant progression of mouse skin tumors.

    PubMed

    Jaffe, D R; Williamson, J F; Bowden, G T

    1987-11-01

    Chemical carcinogenesis in mouse skin has been divided into the process of initiation, promotion and progression. Recently we have shown that ionizing radiation acts as an initiator in this model system. In this paper we describe a three-stage experiment using ionizing radiation in the third stage of mouse skin carcinogenesis. CD-1 mice were initiated with N-methyl-N'-nitro-N-nitrosoguanidine (MNNG) followed by biweekly promotion with 12-O-tetradecanoylphorbol-13-acetate (TPA). After 20 weeks of promotion, the animals were treated with either acetone, TPA (twice a week for 2 weeks) or eight fractions of 1 MeV electrons (1 Gy/fraction over a period of 10 days). The conversion of papillomas to squamous cell carcinomas was 80% for animals treated with ionizing radiation compared with 25% for tumor-bearing animals treated with TPA. Ionizing radiation increased the number of cumulative carcinomas per group. The lack of an increase in the number of cumulative papillomas per group due to ionizing radiation suggests that the dose and fractionation protocol used in this study enhanced the progression of pre-existing papillomas. PMID:3664970

  18. Fundamental studies of matrix-assisted laser desorption/ionization

    SciTech Connect

    Hurst, G.B. [Oak Ridge National Laboratory, TN (United States)

    1994-12-31

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry has been remarkably successful for molecular weight determination of biomolecules. However, the efficiency of ionization, and therefore the sensitivity of the technique, could be improved if details of the ionization mechanism were understood more thoroughly. The chemical and physical environment in the MALDI plume produced by the desorption laser influences the ionization of the analyte, in analogy to the effect of pH on biomolecules in solution. Optical probing techniques, such as laser-induced fluorescence, allow some characteristics of the plume environment to be studied directly. Fluorescence emitted during MALDI experiments using 2,5-dihydroxybenzoic acid (DHB) as the matrix exhibits a broad feature more similar to the emission spectrum of DHB in acidic solution than in neutral or basic solution, suggesting that proton transfer equilibria in the plume can be probed optically. Additionally, narrower features appear in the DHB fluorescence in the MALDI experiment. The origin of these narrow features is not known, but they may be due to emission from small fragments of the matrix, or to cooling of the matrix due to expansion of the plume into the vacuum. In addition to studying the fundamentals of the MALDI ionization mechanism, correlation of plume fluorescence with the efficacy of a given compound as a MALDI matrix may provide a useful optimization tool.

  19. Non-peptide angiotensin II receptor antagonists: chemical feature based pharmacophore identification.

    PubMed

    Krovat, Eva M; Langer, Thierry

    2003-02-27

    Chemical feature based pharmacophore models were elaborated for angiotensin II receptor subtype 1 (AT(1)) antagonists using both a quantitative and a qualitative approach (Catalyst HypoGen and HipHop algorithms, respectively). The training sets for quantitative model generation consisted of 25 selective AT(1) antagonists exhibiting IC(50) values ranging from 1.3 nM to 150 microM. Additionally, a qualitative pharmacophore hypothesis was derived from multiconformational structure models of the two highly active AT(1) antagonists 4u (IC(50) = 0.2 nM) and 3k (IC(50) = 0.7 nM). In the case of the quantitative model, the best pharmacophore hypothesis consisted of a five-features model (Hypo1: seven points, one hydrophobic aromatic, one hydrophobic aliphatic, a hydrogen bond acceptor, a negative ionizable function, and an aromatic plane function). The best qualitative model consisted of seven features (Hypo2: 11 points, two aromatic rings, two hydrogen bond acceptors, a negative ionizable function, and two hydrophobic functions). The obtained pharmacophore models were validated on a wide set of test molecules. They were shown to be able to identify a range of highly potent AT(1) antagonists, among those a number of recently launched drugs and some candidates presently undergoing clinical tests and/or development phases. The results of our study provide confidence for the utility of the selected chemical feature based pharmacophore models to retrieve structurally diverse compounds with desired biological activity by virtual screening. PMID:12593652

  20. Effects of ion-neutral chemical reactions on dynamics of lightning-induced electric field

    NASA Astrophysics Data System (ADS)

    Hiraki, Yasutaka

    2009-08-01

    Secondary lightning phenomena in the upper atmosphere called sprites attract interest from the viewpoint of atomic-molecular and plasma physics. Lightning-induced electric field accelerates the ionospheric electrons up to tens of electron-volts, inducing electrical breakdown as well as strong optical emissions, through electron impact ionization of molecules. A large-scale structure of sprites is constructed by collective dynamics of filamentary streamer discharges in a rarified gas, which in turn is controlled by the distribution of the background electric field. In this paper, we firstly reanalyze the relationship between quasi-static field formation and local ion chemistry with first-order perturbation techniques. Secondly, we investigate with a full ion chemical model the effects of electron attachment to oxygen molecules on its density in moderate cases of undervoltage lightning electric fields rather than the cases of intense ionization in streamers. We estimate the minimum values that are provided by the chemical balance with electron detachment from negative ions. We also investigate the recovery timescale of the electron density and find that the scale (>=1 s) is occasionally much larger than the interval of each lightning stroke (?10 ms). We suggest that the subsequent sprite event as well as the field formation could be well affected by the ghost of the primary event. We discuss further the negative ion chemistry triggered by electron attachment in the nighttime mesosphere.

  1. Argon laser phototherapy could eliminate the damage effects induced by the ionizing radiation “gamma radiation” in irradiated rabbits

    Microsoft Academic Search

    Karolin Kamel Abdul-Aziz; M. J. Tuorkey

    2010-01-01

    The ionizing radiations could be taken in considerate as an integral part in our life, since, living organisms are actually exposed to a constant shower of ionizing radiations whether from the natural or artificial resources. The radio-protective efficiency of several chemicals has been confirmed in animal trails, whereas, due to their accumulative toxicity, their clinical utility is limited. Therefore, we

  2. Carbon-negative biofuels

    Microsoft Academic Search

    John A. Mathews

    2008-01-01

    Current Kyoto-based approaches to reducing the earth's greenhouse gas problem involve looking for ways to reduce emissions. But these are palliative at best, and at worst will allow the problem to get out of hand. It is only through sequestration of atmospheric carbon that the problem can be solved. Carbon-negative biofuels represent the first potentially huge assault on the problem,

  3. Negative Transportation in French.

    ERIC Educational Resources Information Center

    Prince, Ellen F.

    There is a class of verbs in French which require that their complement verb be in the indicative. However, if the matrix clause contains a negative or an interrogative, the complement verb is usually in the subjunctive, but sometimes in the indicative. Examples are the verbs "penser" and "croire" in sentences such as: 1) Elle ne croit pas que…

  4. Negative Binomial Experiment

    NSDL National Science Digital Library

    Kyle Siegrist

    This resource consists of a Java applet and descriptive text. The applet illustrates the number of trials needed to get a specified number of successes in Bernoulli trials, in terms of random points on a discrete timeline. The applet illustrates the negative binomial distribution. The number of successes and the probability of success can be varied.

  5. Anthropological objects and negation

    Microsoft Academic Search

    Marie-Jeanne Borel

    1992-01-01

    Ever since Kant, the possibility of having objects of knowledge has been one of the most basic anthropological questions (“what can I know?”). For the logician, the linguist, or the semiologist who studies natural language, negation is one of these objects. However, as an operation and as a symbol, it has the paradoxical property of not being able to be

  6. The Negative Repetition Effect

    ERIC Educational Resources Information Center

    Mulligan, Neil W.; Peterson, Daniel J.

    2013-01-01

    A fundamental property of human memory is that repetition enhances memory. Peterson and Mulligan (2012) recently documented a surprising "negative repetition effect," in which participants who studied a list of cue-target pairs twice recalled fewer targets than a group who studied the pairs only once. Words within a pair rhymed, and…

  7. Negative pressure wound therapy

    Microsoft Academic Search

    MICHAEL KIRBY

    2010-01-01

    D iabetic foot disease is a major global burden. Foot ulcers frequently develop complications and become chronic, representing a considerable challenge as these are typically very difficult to treat. New therapies are needed to address these wounds and there is an increasing focus on negative pressure wound therapy (NPWT). This technique has been shown to accelerate wound healing and although

  8. Negative pressure wound therapy

    Microsoft Academic Search

    Michael Kirby

    2007-01-01

    iabetic foot disease is a major global burden. Foot ulcers frequently develop complications and become chronic, representing a considerable challenge as these are typically very difficult to treat. New therapies are needed to address these wounds and there is an increasing focus on negative pressure wound therapy (NPWT). This technique has been shown to accelerate wound healing and although its

  9. Negative hydrogen ion emission from heated metal hydride powder

    Microsoft Academic Search

    Hiroyuki Kawano; Hiroshi Nagayasu; Naoshi Serizawa; Hideto Ohta; Makiko Takeda; Motoi Wada; Mamiko Sasao

    1996-01-01

    A small ion source (?2 cm2) of the self-surface negative ionization (SSNI) type was developed to generate H? from a powdery sample (?10 mg) deposited on a molybdenum ribbon (?0.1 cm2). For example, CaH2 heated up to ?900 K emitted ?0.1 nA of H? together with ?1 mA of thermal electrons. The work function of CaH2 was ?6 to 5

  10. Negative ion-atmospheric pressure photoionization-mass spectrometry

    Microsoft Academic Search

    Tiina J. Kauppila; Tapio Kotiaho; Risto Kostiainen; Andries P. Bruins

    2004-01-01

    The ionization mechanism in the novel atmospheric pressure photoionization mass spectrometry (APPI-MS) in negative ion mode\\u000a was studied thoroughly by the analysis of seven compounds in 17 solvent systems. The compounds possessed either gas-phase\\u000a acidity or positive electron affinity, whereas the solvent systems had different polarities and gas-phase acidities and some\\u000a of them positive electron affinities. The analytes that possessed

  11. Quantifying Uranium Isotope Ratios Using Resonance Ionization Mass Spectrometry: The Influence of Laser Parameters on Relative Ionization Probability

    SciTech Connect

    Isselhardt, B H

    2011-09-06

    Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure relative uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process to provide a distinction between uranium atoms and potential isobars without the aid of chemical purification and separation. We explore the laser parameters critical to the ionization process and their effects on the measured isotope ratio. Specifically, the use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of {sup 235}U/{sup 238}U ratios to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a 3-color, 3-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from >10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variation in laser parameters on the measured isotope ratio. This work demonstrates that RIMS can be used for the robust measurement of uranium isotope ratios.

  12. Negative Mass Propulsion

    NASA Astrophysics Data System (ADS)

    Winterberg, F.

    Schrödinger's analysis of the Dirac equation gives a hint for the existence of negative masses hidden behind positive masses. But their use for propulsion by reducing the inertia of matter for example, in the limit of macroscopic bodied with zero rest mass, depends on a technical solution to free them from their imprisonment by positive masses. It appears that there are basically two ways this might be achieved: 1. By the application of strong electromagnetic or gravitational fields or by high particle energies. 2. By searching for places in the universe where nature has already done this separation, and from where the negative masses can be mined. The first of these two possibilities is for all practical means excluded, because if possible at all, it would depend on electromagnetic or gravitational fields with strength beyond what is technically attainable, or on extremely large likewise not attainable particle energies. With regard to the 2nd possibility, it has been observed that non-baryonic cold dark matter tends to accumulate near the center of galaxies, or places in the universe which have a large gravitational potential well. Because of the equivalence principle of general relativity, the attraction towards the center of a gravitational potential well, produced by a positive mass, is for negative masses the same as for positive masses, and large amounts of negative masses might have over billions of years been trapped in these gravitational potential wells. Now it just happens that the center of the moon is a potential well, not too deep that it cannot be reached by making a tunnel through the moon, not possible for the deeper potential well of the earth, where the temperature and pressure are too high. Making a tunnel through the moon, provided there is a good supply of negative mass, could revolutionize interstellar space flight. A sequence of thermonuclear shape charges would make such tunnel technically feasible.

  13. Mathematical Model of DSB formation by Ionizing Radiation

    E-print Network

    Barilla, J; Simr, P

    2008-01-01

    The understanding of inactivation radiobiological mechanism in individual cells is important when from one side the application of ionizing radiation to tumour therapy and from the other side the protection against radiation are to be effectively improved. Important part of this mechanism is double-strand break (DSB) formation; these DSB may be formed directly by impacting ionizing particles or indirectly by different secondary radicals. The latter kind of formation is much more frequent when cells contain normal water content. Mathematical model of the corresponding chemical stage will be presented with the aim to demonstrate how the individual radicals, but also other chemical agents present in the water during irradiation may influence DSB formation.

  14. Negative ions from alkali hydrides as a source for H(-) beams

    NASA Technical Reports Server (NTRS)

    Srivastava, S. K.

    1989-01-01

    The production of H(-) ions by heating LiH powder in a high-temperature crucible was investigated experimentally and theoretically. It is found that the efficiency of H(-) ion production by this method is high. However, the theory for the negative surface ionization indicates that such high efficiency is not possible at crucible temperatures of about 750 C. The need for a further study of LiH ionization is emphasized.

  15. Boron neutron capture therapy of brain tumors: investigation of urinary metabolites and oxidation products of sodium borocaptate by electrospray ionization mass spectrometry.

    PubMed

    Gibson, C R; Staubus, A E; Barth, R F; Yang, W; Kleinholz, N M; Jones, R B; Green-Church, K; Tjarks, W; Soloway, A H

    2001-12-01

    Boron neutron capture therapy (BNCT) is based on a nuclear capture reaction that occurs when boron-10, a stable isotope, is irradiated with low energy neutrons to produce high-energy alpha particles and recoiling lithium-7 nuclei. The purpose of the present study was to determine what urinary metabolites, if any, could be detected in patients with brain tumors who were given sodium borocaptate (BSH), a drug that has been used clinically for BNCT. BSH was infused intravenously over a 1-h time period at doses of 26.5, 44.1, or 88.2 mg/kg of body weight to patients with high-grade brain tumors. Electrospray ionization mass spectrometry has been used to investigate possible urinary metabolites of BSH. Chemical and instrument conditions were established to detect BSH and its possible metabolites in both positive and negative electrospray ionization modes. Using this methodology, boronated ions were found in patients' urine samples that appeared to be consistent with the following chemical structures: BSH sulfenic acid (BSOH), BSH sulfinic acid (BSO(2)H), BSH disulfide (BSSB), BSH thiosulfinate (BSOSB), and a BSH-S-cysteine conjugate (BSH-CYS). Although BSH has been used clinically for BNCT since the late 1960s, this is the first report of specific biotransformation products following administration to patients. Further studies will be required to determine both the biological significance of these metabolites and whether any of these accumulate in significant amounts in brain tumors. PMID:11717178

  16. Flow injection of liquid samples to a mass spectrometer with ionization under vacuum conditions: a combined ion source for single-photon and electron impact ionization.

    PubMed

    Schepler, Claudia; Sklorz, Martin; Passig, Johannes; Famiglini, Giorgio; Cappiello, Achille; Zimmermann, Ralf

    2013-09-01

    Electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photo-ionization (APPI) are the most important techniques for the ionization of liquid samples. However, working under atmospheric pressure conditions, all these techniques involve some chemical rather than purely physical processes, and therefore, side reactions often yield to matrix-dependent ionization efficiencies. Here, a system is presented that combines both soft single-photon ionization (SPI) and hard 70 eV electron impact ionization (EI) of dissolved compounds under vacuum conditions. A quadrupole mass spectrometer was modified to enable direct EI, a technique developed by Cappiello et al. to obtain library-searchable EI mass spectra as well as soft SPI mass spectra of sample solutions. An electron beam-pumped rare gas excimer lamp working at 126 nm was used as well as a focusable vacuum UV light source for single-photon ionization. Both techniques, EI and SPI, were applied successfully for flow injection experiments providing library-matchable EI fragment mass spectra and soft SPI mass spectra, showing dominant signals for the molecular ion. Four model compounds were analyzed: hexadecane, propofol, chlorpropham, and eugenol, with detection limits in the picomolar range. This novel combination of EI and SPI promises great analytical benefits, thanks to the possibility of combining database alignment for EI data and molecular mass information provided by SPI. Possible applications for the presented ionization technology system are a matrix-effect-free detection and a rapid screening of different complex mixtures without time-consuming sample preparation or separation techniques (e.g., for analysis of reaction solutions in combinatorial chemistry) or a switchable hard (EI) and soft (SPI) MS method as detection step for liquid chromatography. PMID:23812882

  17. Effects of ionizing radiation in ginkgo and guarana [rapid communication

    NASA Astrophysics Data System (ADS)

    Rabelo Soriani, Renata; Cristina Satomi, Lucilia; Pinto, Terezinha de Jesus A.

    2005-07-01

    Raw plant materials normally carry high bioburden due to their origin, offering potential hazards to consumers. The use of decontamination processes is therefore an important step towards the consumer safety and therapeutical efficiency. Several authors have reported the treatment of medicinal herbs with ionizing radiation. This work evaluated the effects of different radiation doses on the microbial burden and chemical constituents of ginkgo ( Ginkgo biloba L.) and guaraná ( Paullinia cupana H.B.K.).

  18. The ionization behavior of bile acids in different aqueous environments

    Microsoft Academic Search

    Donna J. Cabral; James A. Hamilton; Donald M. Small

    The ionization behavior of cholic acid, deoxycholic acid, and chenodeoxycholic acid in a variety of physiologically important molecular environments was studied using I3C NMR spectroscopy. The apparent pKa of the carboxyl group was determined from titration curves obtained from the dependence of the carboxyl carbon chemical shift on pH. Using 90% ''C isotopic substitution of the carboxyl carbon, a complete

  19. Sampling a torched planet: MESSENGER observations of Mercury's ionized exosphere

    Microsoft Academic Search

    T. H. Zurbuchen; J. M. Raines; G. Gloeckler; J. A. Slavin; S. M. Krimigis; R. L. McNutt Jr.; M. Sarantos; S. C. Solomon

    2009-01-01

    During its two 2008 flybys, the Fast Imaging Plasma Spectrometer (FIPS) sensor on MESSENGER observed Mercury's ionized exosphere during the probe's passage through the planet's magnetosphere. These unprecedented observations over the range 100 eV\\/e to 14 keV\\/e provide signatures of the intense interactions of the heliospheric space environment with Mercury through ion sputtering, chemical sputtering, and micrometeoroid impact. Ion sputtering

  20. Bichromatic control of photoelectron angular distribution for ionization via intermediate autoionizing states by ultrafast XUV pulses

    NASA Astrophysics Data System (ADS)

    McCurdy, C. William; Li, Xuan; Haxton, Daniel J.

    2014-05-01

    Control of the angular dependence of photoelectrons from ionization of the Li atom by two ultrafast extreme-ultraviolet (XUV) pulses is investigated using an extension of a recently developed implementation of the muticonfiguration time-dependent Hartree Fock (MCTDHF) method. One-photon direct ionization and two-photon ionization via intermediate autoionizing states well above the ionization threshold combine to determine the angular distribution of the ejected photoelectron in these calculations. Two coincident attosecond pulses with different colors provide an opportunity for manipulating the ionization process not available with much longer pulses. It is shown that the resulting asymmetric angular distribution of photoelectrons is sensitive to and can be controlled by the difference between the carrier envelope phases of the two phase-locked XUV pulses of different frequencies. Work supported by USDOE, OBES Chemical Sciences, Geosciences, and Biosciences Division.

  1. Think (Gram) negative!

    PubMed Central

    2010-01-01

    The increasing prevalence of multiresistant Gram-negative bacteria of the Enterobacteriaceae family in Europe is a worrisome phenomenon. Extended spectrum betalactamase-producing Escherichia coli strains are widespread in the community and are frequently imported into the hospital. Of even more concern is the spread of carbapenem-resistant strains of Klebsiella spp. from regions where they are already endemic. Antibiotic use is a main driver of antibiotic resistance, which again increases broad spectrum antibiotic use, resulting in a vicious circle that is difficult to interrupt. The present commentary highlights important findings of a surveillance study of antimicrobial use and resistance in German ICUs over 8 years with a focus on Gram-negative resistance. PMID:20587087

  2. Think (Gram) negative!

    Microsoft Academic Search

    Benedikt Huttner; Stephan Harbarth

    2010-01-01

    The increasing prevalence of multiresistant Gram-negative bacteria of the Enterobacteriaceae family in Europe is a worrisome\\u000a phenomenon. Extended spectrum betalactamase-producing Escherichia coli strains are widespread in the community and are frequently imported into the hospital. Of even more concern is the spread\\u000a of carbapenem-resistant strains of Klebsiella spp. from regions where they are already endemic. Antibiotic use is a main

  3. Algebra Balance Scales - Negatives

    NSDL National Science Digital Library

    Utah State University

    2009-07-01

    This site provides a virtual balance on which the student can represent (and then solve) simple linear equations with integer answers. Conceptually, positive weights (unit-blocks and x-boxes) push the pans of the scale downward. Negative values are represented by balloons which can be attached to the pans of the scale. The student can then manipulate the weights to solve the equation while simultaneously seeing a visual display of these effects on the equation.

  4. Pure ionization cross section of helium and ionization mechanism

    Microsoft Academic Search

    X. M. Chen; Y. X. Lu; Z. M. Gao; Y. Cui; Y. W. Liu; J. Du

    2007-01-01

    Pure target ionization was investigated for 0.4–6.4MeV Cq+(q=1–4)+He and Oq+(q=1–4)+He collisions. The double-to-single target ionization ratios R21 were measured using coincidence techniques. We compare our results with existing experimental results and find they are in good agreement. The ratio R21 is nearly independent of projectile charge state. The relation of R21?V is analyzed using the over barrier model (OBM) and

  5. Neutralization/Ionization of Si Scattered from Adsorbate Sites

    NASA Astrophysics Data System (ADS)

    Chen, Xiaojian; Sroubek, Zdenek; Yarmoff, Jory

    2007-03-01

    In low energy ion scattering, ion-surface charge exchange strongly depends on the surface electronic structure and the ionization level of the projectile. Si has an ionization level that overlaps the center of the surface conduction band and is intermediate in energy to that of alkali ions and noble gas ions, which are the projectiles traditionally used. The scattering of Si thus provides new pathways for ion-surface charge exchange. A considerable fraction of the low energy Si^+ ions backscattered from submonolayers of Cs deposited onto Al(100) are found to be emitted as positive or negative ions. The negative ions result from simple resonant charge transfer (RCT) into the electron affinity level. The formation of Si^+, however, is in contrast to the expected complete neutralization due to the overlap with the surface bands. It is proposed that valence electron RCT enhanced by the interaction of the Si ionization level with the Cs 5p level is responsible for the ion formation. Positive ions were also produced in Si scattered from I adatoms on Al(100), presumably by a similar mechanism. The ion fractions are smaller than those for scattering from Cs, which suggests that electron tunneling from the occupied I chemisorption states provides an additional neutralization channel.

  6. Ontological metaphors for negative energy in an interdisciplinary context

    NASA Astrophysics Data System (ADS)

    Dreyfus, Benjamin W.; Geller, Benjamin D.; Gouvea, Julia; Sawtelle, Vashti; Turpen, Chandra; Redish, Edward F.

    2014-12-01

    Teaching about energy in interdisciplinary settings that emphasize coherence among physics, chemistry, and biology leads to a more central role for chemical bond energy. We argue that an interdisciplinary approach to chemical energy leads to modeling chemical bonds in terms of negative energy. While recent work on ontological metaphors for energy has emphasized the affordances of the substance ontology, this ontology is problematic in the context of negative energy. Instead, we apply a dynamic ontologies perspective to argue that blending the substance and location ontologies for energy can be effective in reasoning about negative energy in the context of reasoning about chemical bonds. We present data from an introductory physics for the life sciences course in which both experts and students successfully use this blended ontology. Blending these ontologies is most successful when the substance and location ontologies are combined such that each is strategically utilized in reasoning about particular aspects of energetic processes.

  7. Structural determination of N-linked glycans by matrix-assisted laser desorption/ionization and electrospray ionization mass spectrometry.

    PubMed

    Harvey, David J

    2005-05-01

    This paper reviews methods for the analysis of N-linked glycans by mass spectrometry with emphasis on studies conducted at the Oxford Glycobiology Institute. Topics covered are the release of glycans from sodium dodecyl sulphate-polyacrylamide gel electrophoresis gels, their purification for analysis by mass spectrometry, methods based on matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization for producing fragment ions, and details of their fragmentation. MALDI mass spectrometry provided a rapid method for profiling neutral N-linked glycans as their [M + Na](+) ions which could be fragmented by collision-induced decomposition to give spectra containing both glycosidic and cross-ring fragments. Electrospray ionization mass spectrometry was more versatile in that it was relatively easy to change the type of ion that was formed and, furthermore, unlike MALDI, electrospray did not cause extensive loss of sialic acids from sialylated glycans. Negative ions formed by addition of anions such as chloride and, particularly, nitrate, to the electrospray solvent were stable and enabled singly charged ions to be obtained from larger glycans than was possible in positive ion mode. Fragmentation of negative ions followed specific pathways that defined structural details of the glycans that were difficult to obtain by classical methods such as exoglycosidase digestion. PMID:15832364

  8. Resonance impact ionization in superlattices

    NASA Astrophysics Data System (ADS)

    Mon, K. K.; Hess, K.

    1982-06-01

    We propose an enhancement of the electron or hole impact ionization coefficients (? or ?) by introducing resonant impact ionization states into the (conduction or valence) band by using suitable lattice matched multilayer heterojunctions (superlattices). Model calculations for the AlAs:GaAs superlattice indicate resonance enhancements can occur over a wide range of energy gaps (1.54-1.9 eV). The gap can be varied by choosing the appropriate ratio of the alternating layer thickness. This effect should be useful for improving the signal/noise ratio of avalanche photodiodes significantly.

  9. Radiative feedback from ionized gas

    E-print Network

    S. C. O. Glover

    2007-03-28

    H2 formation in metal-free gas occurs via the intermediate H- or H2+ ions. Destruction of these ions by photodissociation therefore serves to suppress H2 formation. In this paper, I highlight the fact that several processes that occur in ionized primordial gas produce photons energetic enough to photodissociate H- or H2+ and outline how to compute the photodissociation rates produced by a particular distribution of ionized gas. I also show that there are circumstances of interest, such as during the growth of HII regions around the first stars, in which this previously overlooked form of radiative feedback is of considerable importance.

  10. Ionizing radiation injuries and illnesses.

    PubMed

    Christensen, Doran M; Iddins, Carol J; Sugarman, Stephen L

    2014-02-01

    Although the spectrum of information related to diagnosis and management of radiation injuries and illnesses is vast and as radiation contamination incidents are rare, most emergency practitioners have had little to no practical experience with such cases. Exposures to ionizing radiation and internal contamination with radioactive materials can cause significant tissue damage and conditions. Emergency practitioners unaware of ionizing radiation as the cause of a condition may miss the diagnosis of radiation-induced injury or illness. This article reviews the pertinent terms, physics, radiobiology, and medical management of radiation injuries and illnesses that may confront the emergency practitioner. PMID:24275177

  11. Electron-impact ionization and dissociative ionization of biomolecules

    Microsoft Academic Search

    Winifred Huo

    2006-01-01

    Oxidative damages by ionizing radiation are the source of radiation-induced damages to human health. It is recognized that secondary electrons play a role in the damage process, particularly important is the damage of DNA by electrons, potentially leading to mutagenesis. The damage can be direct, by creating a DNA lesion, or indirect, by producing radicals that attack the DNA. Molecular-level

  12. Chemical Peels

    MedlinePLUS

    ... to Choose the Best Skin Care Products Chemical Peels Uses for Chemical Peels Learn more about specific conditions where chemical peels ... skin Sagging skin Wrinkles What is a chemical peel? A chemical peel is a technique used to ...

  13. Identification of alkylated phosphates by gas chromatography-mass spectrometric investigations with different ionization principles of a thermally aged commercial lithium ion battery electrolyte.

    PubMed

    Weber, Waldemar; Kraft, Vadim; Grützke, Martin; Wagner, Ralf; Winter, Martin; Nowak, Sascha

    2015-05-15

    The thermal aging process of a commercial LiPF6 based lithium ion battery electrolyte has been investigated in view of the formation of volatile phosphorus-containing degradation products. Aging products were analyzed by GC-MS. Structure determination of the products was performed by support of chemical ionization MS in positive and negative modes. A fraction of the discovered compounds belongs to the group of fluorophosphates (phosphorofluoridates) which are in suspect of potential toxicity. This is well known for relative derivatives, e.g. diisopropyl fluorophosphate. Another fraction of the identified compounds belongs to the group of trialkyl phosphates. These compounds may provide a positive impact on the thermal and electrochemical performance of Li-based batteries as repeatedly described in the literature. PMID:25846260

  14. Direct infusion electrospray ionization-ion mobility high resolution mass spectrometry (DIESI-IM-HRMS) for rapid characterization of potential bioprocess streams.

    PubMed

    Munisamy, Sharon M; Chambliss, C Kevin; Becker, Christopher

    2012-07-01

    Direct infusion electrospray ionization?-?ion mobility?-?high resolution mass spectrometry (DIESI-IM-HRMS) has been utilized as a rapid technique for the characterization of total molecular composition in "whole-sample" biomass hydrolysates and extracts. IM-HRMS data reveal a broad molecular weight distribution of sample components (up to 1100 m/z) and provide trendline isolation of feedstock components from those introduced "in process." Chemical formulas were obtained from HRMS exact mass measurements (with typical mass error less than 5 ppm) and were consistent with structural carbohydrates and other lignocellulosic degradation products. Analyte assignments are supported via IM-MS collision-cross-section measurements and trendline analysis (e.g., all carbohydrate oligomers identified in a corn stover hydrolysate were found to fall within 6% of an average trendline). These data represent the first report of collision cross sections for several negatively charged carbohydrates and other acidic species occurring natively in biomass hydrolysates. PMID:22592813

  15. Cesium Delivery System for Negative Ion Source at IPR

    SciTech Connect

    Bansal, G.; Pandya, K.; Soni, J.; Gahlaut, A.; Parmar, K. G. [Institute for Plasma Research, Bhat, Gandhinagar, Gujarat, 382 428 (India); Bandyopadhyay, M.; Chakraborty, A.; Singh, M. J. [ITER- India, Institute for Plasma Research, A-29, Sector 25, GIDC, Gandhinagar, Gujarat (India)

    2011-09-26

    The technique of surface production of negative ions using cesium, Cs, has been efficiently exploited over the years for producing negative ion beams with increased current densities from negative ion sources used on neutral beam lines. Deposition of Cs on the source walls and the plasma grid lowers the work function and therefore enables a higher yield of H{sup -}, when hydrogen particles (H and/or H{sub x}{sup +}) strike these surfaces.A single driver RF based (100 kW, 1 MHz) negative ion source test bed, ROBIN, is being set up at IPR under a technical collaboration between IPR and IPP, Germany. The optimization of the Cs oven design to be used on this facility as well as multidriver sources is underway. The characterization experiments of such a Cs delivery system with a 1 g Cs inventory have been carried out using surface ionization technique. The experiments have been carried by delivering Cs into a vacuum chamber without plasma. The linear motion of the surface ionization detector, SID, attached with a linear motion feedthrough allows measuring the angular distribution of the Cs coming out of the oven. Based on the experimental results, a Cs oven for ROBIN has been proposed. The Cs oven design and experimental results of the prototype Cs oven are reported and discussed in the paper.

  16. Ionization of CF3I

    NASA Astrophysics Data System (ADS)

    Jiao, C. Q.; Garscadden, A.; Ganguly, B.; Dejoseph, C. A., Jr.

    2000-10-01

    Using Fourier-transform mass spectrometry we have studied the ionization of trifluoroiodomethane (CF_3I) by electron impact and by ion-molecule reactions. Electron impact ionization on CF_3I produces molecular ion CF_3I^+ and fragment ions including I^+, CF_3^+, CF_2I^+, CF^+, CF_2^+ and CI^+, with a total cross-section of 9.0±0.9x10-16 cm^2 at 70 eV. The parent molecular ion dominates the ion population within the energy range studied (from the threshold to 70 eV). At low electron energies (less than 20 eV) the most important dissociative ionization channel is the production of CF_3^+ and I. In contrast ionization of CF_3I by charge-transfer reaction with Ar^+ produces CF_2I^+ as the major product ion, with a rate coefficient of 14x10-10 cm^3s-1. The CF_3I reaction with CF^+ or CF_3^+ produces CF_2I^+ mainly also, with the rate coefficients 5.8 or 1.9 x10-10 cm^3s-1, respectively, while the reaction with CF_2^+ or I^+ produces primarily CF_3I^+, with the rate coefficients of 13 or 8.2 x10-10 cm^3s-1, respectively.

  17. CEILCOTE IONIZING WET SCRUBBER EVALUATION

    EPA Science Inventory

    The report gives results of an evaluation of a Ceilcote ionizing wet scrubber installed on a refractory brick kiln. Tests involved particulate mass emission, particle size distribution, and opacity. Overall efficiency was 93% with an average outlet opacity determined with a heate...

  18. Ionization Potentials for Isoelectronic Series.

    ERIC Educational Resources Information Center

    Agmon, Noam

    1988-01-01

    Presents a quantitative treatment of ionization potentials of isoelectronic atoms. By looking at the single-electron view of calculating the total energy of an atom, trends in the screening and effective quantum number parameters are examined. Approaches the question of determining electron affinities. (CW)

  19. Low-level ionizing radiation and human leukemia: Juvenile and adult dichotomy. Technical report, January 1984-April 1986

    SciTech Connect

    Bowers, E.J.; Zemel, B.S.; Hickey, R.J.; Allen, I.E.; Junker, L.L.

    1985-01-01

    Human leukemia mortality rates for 43 urban populations (cities) of the United States, 1957-1964, were analyzed against several environmental variables using mean annual rates per 100,000 persons for all ages, and for two age subsets. One subset involves rates for persons <25 years; the other involves rates for persons >25 years. Among environmental variables examined were natural background levels of ionizing radiation (RA); mean atmospheric concentrations of several common air pollutant chemicals, and several socio-economic variables. A statistically significant positive correlation was found between RA level and leukemia mortality rate for those <25 years of age. In contrast, for those >25 years, the correlation was weak and negative. Comparably, the correlation between atmospheric vanadium levels and leukemia mortality rates for those <25 years was significantly negative, while the correlation with rates for those >25 years was significantly positive. Other such contrasts were found, as for atmospheric nickel and for sulfate, and for water hardness. Such results are compatible with findings of others, and support the hypothesis that the etiologies of juvenile and adult-onset leukemias are quite different. Possible foundations for these differences are considered.

  20. Ionizing air affects influenza virus infectivity and prevents airborne-transmission.

    PubMed

    Hagbom, Marie; Nordgren, Johan; Nybom, Rolf; Hedlund, Kjell-Olof; Wigzell, Hans; Svensson, Lennart

    2015-01-01

    By the use of a modified ionizer device we describe effective prevention of airborne transmitted influenza A (strain Panama 99) virus infection between animals and inactivation of virus (>97%). Active ionizer prevented 100% (4/4) of guinea pigs from infection. Moreover, the device effectively captured airborne transmitted calicivirus, rotavirus and influenza virus, with recovery rates up to 21% after 40?min in a 19?m(3) room. The ionizer generates negative ions, rendering airborne particles/aerosol droplets negatively charged and electrostatically attracts them to a positively charged collector plate. Trapped viruses are then identified by reverse transcription quantitative real-time PCR. The device enables unique possibilities for rapid and simple removal of virus from air and offers possibilities to simultaneously identify and prevent airborne transmission of viruses. PMID:26101102

  1. Ionizing air affects influenza virus infectivity and prevents airborne-transmission

    PubMed Central

    Hagbom, Marie; Nordgren, Johan; Nybom, Rolf; Hedlund, Kjell-Olof; Wigzell, Hans; Svensson, Lennart

    2015-01-01

    By the use of a modified ionizer device we describe effective prevention of airborne transmitted influenza A (strain Panama 99) virus infection between animals and inactivation of virus (>97%). Active ionizer prevented 100% (4/4) of guinea pigs from infection. Moreover, the device effectively captured airborne transmitted calicivirus, rotavirus and influenza virus, with recovery rates up to 21% after 40?min in a 19?m3 room. The ionizer generates negative ions, rendering airborne particles/aerosol droplets negatively charged and electrostatically attracts them to a positively charged collector plate. Trapped viruses are then identified by reverse transcription quantitative real-time PCR. The device enables unique possibilities for rapid and simple removal of virus from air and offers possibilities to simultaneously identify and prevent airborne transmission of viruses. PMID:26101102

  2. Carbon nanotube-based field ionization vacuum

    E-print Network

    Jang, Daniel, M. Eng. Massachusetts Institute of Technology

    2012-01-01

    We report the development of a novel micropump architecture that uses arrays of isolated vertical carbon nanotubes (CNT) to field ionize gas particles. The ionized gas molecules are accelerated to and implanted into a ...

  3. Detection of positive and negative ions from a flowing atmospheric pressure afterglow using a mattauch-herzog mass spectrograph equipped with a faraday-strip array detector

    Microsoft Academic Search

    Gregory D. Schilling; Jacob T. Shelley; James H. Barnes IV; Roger P. Sperline; M. Bonner Denton; Charles J. Barinaga; David W. Koppenaal; Gary M. Hieftje

    2010-01-01

    An ambient desorption\\/ionization (ADI) source, known as the flowing atmospheric pressure afterglow (FAPA), has been coupled\\u000a to a Mattauch-Herzog mass spectrograph (MHMS) equipped with a focal plane camera (FPC) array detector. The FAPA ionization\\u000a source enables direct mass spectral analysis of solids, liquids, and gases through either positive or negative ionization\\u000a modes. In either case, spectra are generally simple with

  4. NON-CHEMICAL IMPACTS (SYSTEMS ANALYSIS BRANCH, SUSTAINABLE TECHNOLOGY DIVISION, NRMRL)

    EPA Science Inventory

    Non-chemical ecological impacts include those that are caused by physical or biological disturbances. Non-chemical stressors identified by SETAC include ionizing radiation, heat, noise, environmental disturbances (habitat alteration, including changes to biochemical cycling, biod...

  5. Curvature and ionization-induced reversible hydrogen storage in metalized hexagonal B36.

    PubMed

    Liu, Chun-Sheng; Wang, Xiangfu; Ye, Xiao-Juan; Yan, Xiaohong; Zeng, Zhi

    2014-11-21

    The synthesis of quasiplanar boron clusters (B36) with a central hexagonal hole provides the first experimental evidence that a single-atomic-layer borophene with hexagonal vacancies is potentially viable [Z. Piazza, H. Hu, W. Li, Y. Zhao, J. Li, and L. S. Wang, Nat. Commun. 5, 3113 (2014)]. However, owing to the hexagonal holes, tunning the electronic and physical properties of B36 through chemical modifications is not fully understood. Based on (van der Waals corrected-) density functional theory, we show that Li adsorbed on B36 and B36 (-) clusters can serve as reversible hydrogen storage media. The present results indicate that the curvature and ionization of substrates can enhance the bond strength of Li due to the energetically favorable B 2p-Li 2p orbitals hybridization. Both the polarization mechanism and the orbital hybridization between H-s orbitals and Li-2s2p orbitals contribute to the adsorption of H2 molecules and the resulting adsorption energy lies between the physisorbed and chemisorbed states. Interestingly, the number of H2 in the hydrogen storage medium can be measured by the appearance of the negative differential resistance behavior at different bias voltage regions. Furthermore, the cluster-assembled hydrogen storage materials constructed by metalized B36 clusters do not cause a decrease in the number of adsorbed hydrogen molecules per Li. The system reported here is favorable for the reversible hydrogen adsorption/desorption at ambient conditions. PMID:25416890

  6. Microchip capillary electrophoresis-electrospray ionization-mass spectrometry of intact proteins using uncoated Ormocomp microchips.

    PubMed

    Sikanen, Tiina; Aura, Susanna; Franssila, Sami; Kotiaho, Tapio; Kostiainen, Risto

    2012-01-20

    We present rapid (<5 min) and efficient intact protein analysis by mass spectrometry (MS) using fully microfabricated and monolithically integrated capillary electrophoresis-electrospray ionization (CE-ESI) microchips. The microchips are fabricated fully of commercial inorganic-organic hybrid material, Ormocomp, by UV-embossing and adhesive Ormocomp-Ormocomp bonding (CE microchannels). A sheath-flow ESI interface is monolithically integrated with the UV-embossed separation channels by cutting a rectangular emitter tip in the end with a dicing saw. As a result, electrospray was produced from the corner of chip with good reproducibility between parallel tips (stability within 3.8-9.2% RSD). Thanks to its inherent biocompatibility and stable (negative) surface charge, Ormocomp microchips enable efficient intact protein analysis with up to ?10(4) theoretical separation plates per meter without any chemical or physical surface modification before analysis. The same microchip setup is also feasible for rapid peptide sequencing and mass fingerprinting and shows excellent migration time repeatability from run to run for both peptides (5.6-5.9% RSD, n=4) and intact proteins (1.3-7.5% RSD, n=3). Thus, the Ormocomp microchips provide a versatile new tool for MS-based proteomics. Particularly, the feasibility of the Ormocomp chips for rapid analysis of intact proteins with such a simple setup is a valuable increment to the current technology. PMID:22152798

  7. Comparison of extraction techniques and mass spectrometric ionization modes in the analysis of wine volatile carbonyls.

    PubMed

    Zapata, Julián; Mateo-Vivaracho, Laura; Cacho, Juan; Ferreira, Vicente

    2010-02-15

    This work presents a comparative study of the analytical characteristics of two methods for the analysis of carbonyl compounds in wine, both based on the derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA). In the first method derivatives are formed in the solid phase extraction (SPE) cartridge in which the analytes have been previously isolated, while in the second method derivatives are formed in a solid phase microextraction (SPME) fibre saturated with vapors of the reagent and exposed to the sample headspace. In both cases detection has been carried out by electron impact (EI) or negative chemical ionization (NCI) mass spectrometry. The possibility of determining haloanisols simultaneously has been also considered. The method based on SPE presents, in general, better analytical properties than the SPME one. Although linearity was satisfactory for both methods (R(2)>0.99), repeatability of the SPE method (RSD<10%) was better than that obtained with SPME (9% < RSD < 20%). Detection limits obtained with EI are better for the SPE method except for trihaloanisols, while with NCI detection limits for both strategies are comparable, although the SPME strategy presents worse results for ketones and methional. Detection limits are always lower with NCI, being the improvement most notable for SPME. Recovery experiments show that in the case of SPE, uncertainties are lower than 12% in all cases, while with the SPME method the imprecision plus the existence of matrix effects make the global uncertainty to be higher than 15%. PMID:20103163

  8. Negative Ions for Emerging Interdisciplinary Applications

    NASA Astrophysics Data System (ADS)

    Guharay, Samar K.

    2011-09-01

    In many applications related to ion beam-materials interactions negative ions are particularly desirable due to its merit to yield a very low surface charge-up voltage, ˜ a few volts, for both electrically isolated surfaces and insulators. Some important applications pertaining to ion beam-material interactions include surface analysis by secondary ion mass spectrometry (SIMS), voltage-contrast microscopy for semiconductor device inspection, materials processing, and ion beam lithography. These applications primarily require vacuum environments. On the other hand, a distinct area of activities constitutes formation of ions and ion transport in ambient environmental conditions, i.e., at atmospheric pressures. In this context, ion mobility spectrometry (IMS) is an important analytical device that uses negative ions and operates at ambient conditions. IMS is widely used in both physical and biological sciences including monitoring environmental conditions, security screening and disease detection. This article highlights several critical issues related to the ionization sources and ion transport in IMS. Additionally, the critical issues related to ion sources, transport and focusing are discussed in the context of SIMS with sub-micrometer spatial resolution.

  9. Negative Ions for Emerging Interdisciplinary Applications

    SciTech Connect

    Guharay, Samar K. [MITRE Corporation, 7515 Colshire Dr., MS H407, McLean, VA 22102 (United States)

    2011-09-26

    In many applications related to ion beam-materials interactions negative ions are particularly desirable due to its merit to yield a very low surface charge-up voltage, {approx} a few volts, for both electrically isolated surfaces and insulators. Some important applications pertaining to ion beam-material interactions include surface analysis by secondary ion mass spectrometry (SIMS), voltage-contrast microscopy for semiconductor device inspection, materials processing, and ion beam lithography. These applications primarily require vacuum environments. On the other hand, a distinct area of activities constitutes formation of ions and ion transport in ambient environmental conditions, i.e., at atmospheric pressures. In this context, ion mobility spectrometry (IMS) is an important analytical device that uses negative ions and operates at ambient conditions. IMS is widely used in both physical and biological sciences including monitoring environmental conditions, security screening and disease detection. This article highlights several critical issues related to the ionization sources and ion transport in IMS. Additionally, the critical issues related to ion sources, transport and focusing are discussed in the context of SIMS with sub-micrometer spatial resolution.

  10. Negative Ion Excited States

    NASA Astrophysics Data System (ADS)

    Mead, Roy D.

    This dissertation describes high-resolution tunable laser photodetachment studies of both valence and dipole -bound excited states of negative ions. Also discussed is a merged laser-ion beam photodetachment spectrometer. The photodetachment cross section of C(,2)('-) displays many sharp resonances, due to excitation of autodetaching levels of the B('2)(SIGMA)(,u)('+) valence state lying above the onset of the (C(,2) + e) continuum. The positions of approximately 1,000 resonances were measured, allowing the spectroscopic constants of the ground X('2)(SIGMA)(,g)('+) and excited B('2)(SIGMA)(,u)('+) states to be determined, including spin-rotation constants. The previously unobserved A('2)(PI)(,u) state has been characterized by deperturbation analysis. Strong A-X transitions are predicted near 2.5 microns. The widths of C(,2)('-) resonances with v = 6 -10 and J = 1-60 have also been measured, providing autodetachment rates as a function of both rotation and vibration, ranging from 10('8) to 10('11) s('-1). The first conclusive observation of an entirely new class of states, called dipole-bound or dipole-supported states, is discussed for the case of acetaldehyde enolate (vinyl oxide) negative ion. In these novel states, the extra electron is weakly bound ((TURN)5 cm('-1)) in a very diffuse orbital ((TURN)100 (ANGSTROM)) by the dipole moment of the neutral core. Weak electric fields (< 70 V/cm) are found to rapidly detach the dipole-bound electron. These dipole-bound states resemble Rydberg states of neutrals, but differ from Rydbergs in many important respects. They should be present for all neutrals with dipole moments > 2 Debye. The merged laser-ion beam (also known as coaxial -beams) spectrometer has 0.0005 cm('-1) resolution in the visible region, simultaneously achieving very high sensitivity. It employs quadrupole beam deflectors to merge and laser and negative ion beams, and can scan spectra either by scanning the laser frequency or the Doppler shift of the ion beam. Both electrons and neutral photodetachment products are detected. Even very low energy electrons (< 20 meV) are collected and counted, and the collector may be adjusted to collect either all electrons or only low energy electrons as needed.

  11. Chemical Changes

    NSDL National Science Digital Library

    Mr. Jolley

    2005-10-25

    In this activity you will learn what a chemical change is. The first step to understanding chemical changes is to recognize the difference between chemical properties and physical properties. Click here for an example: Chemical and Physical Changes What are the signs of a chemical reaction occuring? Signs of Chemical Change What variables affect a chemical reaction? Variables ...

  12. The effects of ionization on the jump conditions for MHD and transverse ionizing shock waves

    Microsoft Academic Search

    R. C. Cross; C. D. Mathers

    1979-01-01

    The jump conditions for MHD shock waves in partly ionized gases and for transverse ionizing shock waves in neutral gases are obtained in explicit forms suitable for calculation. The fractional ionization behind the shock front is determined by assuming the plasma reaches Saha ionizational equilibrium. Solutions to the MHD jump equations are calculated for geometries ranging from transverse to switch-on.

  13. Negation, Polarity, and Deontic Modals

    E-print Network

    Iatridou, Sabine

    Universal deontic modals may vary with respect to whether they scope over or under negation. For instance, English modals like must and should take wide scope with respect to negation; modals like have to and need to take ...

  14. A marginal theory for critical velocity ionization

    Microsoft Academic Search

    D. L. Cooke; L. W. Wright; T. C. Genoni; R. J. Biasca

    1995-01-01

    Summary form only given. All space based tests of Alfven's critical velocity ionization (CIV) hypothesis to date may be described as marginal. That is, no large excess of ionization has been observed, but in many experiments, such as Porcupine, the observed ionization seems to exceed that which can be explained by charge exchange and other collisional processes. This talk will

  15. Computer simulation of critical velocity ionization

    Microsoft Academic Search

    Shinobu Machida; Takashi Abe; Toshio Terasawa

    1984-01-01

    The mechanism of critical velocity ionization is studied through electrostatic particle simulations which include a neutral-particle ionization process. It is shown that the rapid ionization of neutral particles takes place when the flow velocity of the neutral particles across a magnetic field exceeds a certain threshold. The mechanism is explained in terms of lower-hybrid wave excitation by a plasma instability,

  16. Calculated ionization potentials for multiply charged ions

    Microsoft Academic Search

    T. A. Carlson; C. W. Jr. Nestor; N. Wasserman; J. D. McDowell

    1970-01-01

    Ionization potentials were calculated for all the elements up to Z = 103 ; for all states of ionization. The calculations are based on a simple spherical ; shell solution for neutral atoms. The average deviation of the calculated ; ionization potentials from experimental values was found to be about 5%. A ; simple method is also given for estimating

  17. Radio Communication by Scattering from Meteoric Ionization

    Microsoft Academic Search

    Von Eshleman; Laurence Manning

    1954-01-01

    By a consideration of the amplitude and duration of echoes forward-scattered from individual meteor ionization trails, and of the probability of detecting randomly oriented trails over an oblique radio propagation path, an estimate of the contribution of meteoric ionization to extended range hf and vhf radio transmission has been obtained. It has been concluded that meteoric ionization alone would give

  18. An experimental investigation of ionization of supersonic air by a corona discharge

    NASA Astrophysics Data System (ADS)

    Satyanand, Udyavar S.

    A technique is developed to ionize supersonic air flow in a shock tube by a weak corona discharge. The driven section of the tube is open to the atmosphere. The shock propagates in the driven section at about 1 km/s by means of an area contraction near the downstream end of the driven section. Air is ionized by a unipolar corona discharge device comprising of a sharp-edged wedge as a high-field electrode inserted in a 41.25 mm (2") ID tube that forms a low-field electrode. The device requires less than 0.5 W. A ring probe, downstream of the corona discharge device, collects charges (ions and electrons) from the air; its output voltage is thus a measure of the degree of ionization. The degree of ionization is varied by varying the corona discharge voltage and the flow speed. Corona generation was initially demonstrated with bench tests. These indicated an increased degree of ionization with an air flow created by a fan, relative to that in static air. Tests in a shock tube, with subsonic and supersonic air flow, and with a negative corona, provided results with the same ionization behavior. The operating range of discharge voltages is relatively small for a positive corona; hence, shock tube tests were confined to a negative corona. Shock tube test results indicate that, on a 10 millisecond time scale, corona generated ionization was convected downstream to the probe location in a supersonic flow. An anomalous shock tube result is a probe signal, without a corona discharge, that is similar, but weaker, to the signal with a discharge. Although the tests were done with shock speeds up to about 1 km/s and with atmospheric air ahead of shock wave, the technique of ionization and plasma measurement can be extended to higher speeds and lower pressures. It is also suggested that a supersonic wind tunnel with a Langmuir probe be used for this type of work.

  19. Differentiation of isomeric substituted diaryl ethers by electron ionization and chemical ionization mass spectrometry.

    PubMed

    Bhaskar, G; Prabhakar, S; Venkat Narsaiah, A; Nagaiah, K; Ramanjaneyulu, G S; Vairamani, M

    2006-01-01

    A series of isomeric substituted diaryl ethers, i.e., 2- or 4-NO2, 5- FC6H3OC6H4 (4-R), where R=H, COCH3, COOCH3, NO2, CHO, OCH3 etc., which comprise ortho and para isomers with respect to the position of the nitro group are studied under GC-EI-MS and CI-MS conditions. The EI mass spectra of ortho and para isomers show distinct fragment ions, where the [MOH]+ and [MOHO]+ ions specifically appeared in all spectra of the ortho isomers (I), whereas the para isomers (II) contain [MO]+ and [MNO]+ ions. The [MOHCO]+ and [MOHNO]+ ions in I, and [MNO2]+ ion in II are the other specific fragment ions observed but feasibility of these fragment ions are found to depend on the nature of the substituent (R). The substitution (R) effect is also clearly reflected in the formation of fragment ions due to sigma-cleavage process with or without hydrogen migration. Similar differences in the formation of specific fragment ions are also observed in ortho and para isomers of substituted aryl naphthyl ethers. The methane/CI of isomeric compounds resulted in the same set of fragment ions, but prominent differences are observed in the relative abundance of [MHNO]+, which is relatively higher in para isomers compared with corresponding ortho isomer. PMID:16819107

  20. Asymptotic behaviour of reversible chemical reaction-diffusion equations

    E-print Network

    Paris-Sud XI, Université de

    Asymptotic behaviour of reversible chemical reaction-diffusion equations Ivan Gentil and Boguslaw chemical reaction-diffusion equations with the same diffusion. In particular we prove the optimal rate40, 35A05, 35F25 1 Introduction The self-ionization of water is the chemical reaction in which two