Sample records for negative chemical ionization

  1. NEGATIVE CHEMICAL IONIZATION STUDIES OF HUMAN AND FOOD CHAIN CONTAMINATION WITH XENOBIOTIC CHEMICALS

    EPA Science Inventory

    Negative chemical ionization mass spectrometry with a mixture of isobutane, methylene chloride, and oxygen as the reagent gas has been used to explore contamination of environmental substrates with xenobiotic chemicals. The substrates in question, fish tissue, human seminal plasm...

  2. 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

  3. Negative chemical ionization studied of human and food chain contamination with xenobiotic chemicals.

    PubMed Central

    Dougherty, R C; Whitaker, M J; Smith, L M; Stalling, D L; Kuehl, D W

    1980-01-01

    Negative chemical ionization mass spectrometry with a mixture of isobutane, methylene chloride, and oxygen as the reagent gas has been used to explore contamination of environmental substrates with xenobiotic chemicals. The substrates in question, fish tissue, human seminal plasma, and human adipose tissue, were cleaned up by one of the following three cleanup procedures: (1) continuous liquid-liquid extraction steam distillation; (2) gel-permeation chromatography; and (3) adsorption on activated carbon followed by elution with toluene. The third procedure was used only for the examination of planar polychlorinated aromatic hydrocarbons in environmental samples. Using these techniques, we have found evidence for contamination of fish samples with polychloronaphthalenes, polychlorostyrenes, polychlorobiphenyls, polychlorodibenzofurans, and polychlorodibenzodioxins among other chemicals. The polychlorodibenzodioxins appeared only in the spectra of extracts of fish obtained from the Tittabawassee River at Midland Michigan. The polychlorodibenzofuran ions appeared in NCI mass spectra of fish that were significantly contaminated (above 2 ppm) with polychlorobiphenyls. Toxic substances occurring in human seminal plasma included pentachlorophenol, hexachlorobenzene, DDT metabolites, and polychlorobiphenyls. We have investigated toxic substances in human seminal plasma because of the apparent decrease in sperm density in U.S. males over the last 30 years. Results of screening human adipose tissue for contamination with xenobiotic chemicals have been largely coincident with result of the EPA human monitoring program. Polychlorobiphenyls, DDT metabolites, nonachlor, and chlordane have appeared in most samples examined. Detection limits for all of these chemicals were of the order of 1 ppb. PMID:7428739

  4. ELECTRON AFFINITIES OF POLYNUCLEAR AROMATIC HYDROCARBONS AND NEGATIVE ION CHEMICAL IONIZATION SENSITIVITIES

    EPA Science Inventory

    Negative-ion chemical-ionization mass spectrometry (NICI MS) has the potential to be a very useful technique in identifying various polycyclic aromatic hydrocarbons (PAHs) in soil and sediment samples. Some PAHs give much stronger signals under NICI MS conditions than others. On ...

  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. Hair analysis for nordiazepam and oxazepam by gas chromatography-negative-ion chemical ionization mass spectrometry

    Microsoft Academic Search

    Pascal Kintz; Vincent Cirimele; François Vayssette; Patrice Mangin

    1996-01-01

    A procedure is presented for the identification of nordiazepam and its metabolite, oxazepam, in human hair. The method involves decontamination of hair with dichloromethane, incubation in phosphate buffer (pH 7.6) in the presence of deuterated internal standards, liquid-liquid extraction, derivatization with N,O-bis(trimethylsilyl)trifluoroacetamide plus 1% trimethylchlorosilane and gas chromatography-mass spectrometry using negative-ion chemical ionization with methane. Among thirty samples obtained from

  8. Electron impact, electron capture negative ionization and positive chemical ionization mass spectra of organophosphorus flame retardants and plasticizers.

    PubMed

    Ma, Yuning; Hites, Ronald A

    2013-08-01

    Phosphate esters are important commercial products that have been used both as flame retardants and as plasticizers. To analyze these compounds by gas chromatographic mass spectrometry, it is important to understand the mass spectra of these compounds using various ionization modes. This paper is a systematic overview of the electron impact (EI), electron capture negative ionization (ECNI) and positive chemical ionization (PCI) mass spectra of 13 organophosphate esters. These data are useful for developing and optimizing analytical measurements. The EI spectra of these 13 compounds are dominated by ions such as H4 PO4 (+) , (M?-?Cl)(+) , (M?-?CH2 Cl)(+) or (M)(+) depending on specific chemical structures. The ECNI spectra are generally dominated by (M?-?R)(-) . The PCI spectra are mainly dominated by the protonated molecular ion (M?+?H)(+) . The branching of the alkyl substituents, the halogenation of the substituents and, for aromatic phosphate esters, ortho alkylation of the ring are all significant factors controlling the details of the fragmentation processes. EI provides the best sensitivity for the quantitative measurement of these compounds, but PCI and ECNI both have considerable qualitative selectivity. PMID:23893640

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

    PubMed

    Laakso, P; Kallio, H

    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 ionized, using the reactant gas pressure of approximately 8500 mtorr at the ion source temperature of 200 degrees C with the instrumentation used. Abundant [M-H]- ions were produced under these conditions without the formation of [M + 35]- cluster ions, which would interfere with the molecular weight region of triacylglycerols in the spectra. A rapid desorption of the sample from the probe wire is recommended, using a relatively high heating rate (approximately 40 mA s-1), to minimize thermal degradation of unsaturated molecules and the reducing effect of double bonds on the mass spectrometric response of triacylglycerols. Furthermore, the abundance of [M-H]- ion was enhanced by rapid heating, which we found to be important to improve the sensitivity. The appropriate amount of sample applied to the rhenium wire was in the region of 50-300 ng for one determination, i.e., only a few nanograms of a single triacylglycerol is required for production of a reliable spectrum. The reproducibility of the method was good as demonstrated with standards and a raspberry seed oil sample. The described mass spectrometric method is a fast and potentially useful tool for semiquantitative determination of triacylglycerol mixtures of various fats and oils. The discrimination, caused by differences in molecular size and unsaturation of triacylglycerols with 50 to 56 acyl carbons, was negligible under our optimized ionization conditions, thus, no correction factors were needed. These findings have not yet been verified with instruments in other laboratories. However, the present study shows how the analysis of triacylglycerols can be improved, regardless of the instrument, by optimization of the analytical conditions. PMID:8649231

  10. Determination of BROMATE AT PARTS-PER-TRILLION LEVELS BY GAS CHROMATOGRAPHY-MASS SPECTROMETRY WITH NEGATIVE CHEMICAL IONIZATION

    EPA Science Inventory

    The ozonation of bromide-containing source waters produces bromate as a class 2B carcinogenic disinfection by-product. The present work describes the determination of bromate by gas chromatography-negative chemical ionization mass spectrometry (GC-NCIMS) following a bromate react...

  11. Negative ion chemical ionization gas chromatography/mass spectrometry of valproic acid metabolites.

    PubMed

    Kassahun, K; Burton, R; Abbott, F S

    1989-10-01

    A negative ion chemical ionization (NICI) gas chromatographic/mass spectrometric method is described for the identification of 15 valproic acid (VPA) metabolites as their pentafluorobenzyl derivatives. Samples analyzed were serum, urine and saliva taken from a volunteer on VPA at steady state and also given selected doses of (2H6)VPA. Metabolite peaks were identified by comparison to synthetic standards. All the metabolites, like the parent drug, produced abundant [M - 181]- ions, except 3-keto VPA, which gave an [M - 181 - CO2]- ion. Using the NICI method, two new VPA metabolites were identified. One of these metabolites was characterized as 4'-keto-2-ene VPA by synthesis, while the second one appeared to be a positional isomer of 4'-keto-2-ene VPA. The sensitivity of the method was also sufficient to detect metabolites of VPA in saliva. The ratio of the levels of (Z)-2-ene VPA to (E)-2-ene VPA was much greater in saliva than in serum, suggesting stereoselective plasma protein binding or transport of these two metabolites. The lower limit of detection for the quantification of VPA in serum or saliva was 2 ng ml-1. PMID:2508808

  12. 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

    2014-12-01

    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

  13. The quantitation of triazolam in postmortem blood by gas chromatography/negative ion chemical ionization mass spectrometry.

    PubMed

    Koves, G; Wells, J

    1986-01-01

    A specific and sensitive assay has been developed to quantitate triazolam in postmortem blood using 2H6-triazolam as an internal standard. Triazolam is isolated from whole blood by adsorption on an Amberlite XAD-2 resin and subsequent elution with an organic solvent. The extract is analyzed by gas chromatography/mass spectometry using selected ion monitoring (GC/MS/SIM) in the negative chemical ionization mode (Cl-). The procedure is presently being used in case work and the results from 36 cases are presented. PMID:3807323

  14. Confirmation of avermectin residues in food matrices with negative-ion atmospheric pressure chemical ionization liquid chromatography/mass spectrometry.

    PubMed

    Turnipseed, S B; Roybal, J E; Rupp, H S; Gonzales, S A; Pfenning, A P; Hurlbut, J A

    1999-01-01

    A multi-residue LC/MS method has been developed to confirm avermectin drug residues in several food matrices. Ivermectin (IVR), doramectin (DOR), eprinomectin (EPR) and moxidectin (MOX) are confirmed using atmospheric pressure chemical ionization (APCI) with negative ion detection and selected ion monitoring of three to four ions for each compound. The drug residues are extracted from tissue or milk using previously published procedures. IVR and DOR are confirmed at 20 ppb levels in fortified salmon muscle; IVR is also confirmed in tissue from salmon dosed with the drug. Residues of DOR, IVR, and EPR are confirmed in fortified milk at the 20 ppb level and in fortified beef liver at 40 ppb. Residues of MOX can also be confirmed in these matrices, but at slightly higher levels (40-80 ppb). PMID:10204245

  15. MICROMETHODS FOR TOXIC RESIDUE SCREENING BY NEGATIVE CHEMICAL IONIZATION MASS SPECTROMETRY

    EPA Science Inventory

    Methods were developed for the analysis of polychlorinated chemical residues found in milligram quantities of biological samples. Sample preparation by micro-continuous liquid-liquid extraction steam distillation or by micro gel-permeation chromatography gave sufficiently clean r...

  16. Confirmation of clorsulon residues in cattle kidney by capillary gas chromatography-negative-ion chemical-ionization mass spectrometry.

    PubMed

    Wehner, T A; Wood, J S; Walker, R; Downing, G V; Vandenheuvel, W J

    1987-07-24

    A confirmatory assay for residues of the anthelmintic agent clorsulon [4-amino-6-(trichloroethenyl)-1,3-benzenedisulfonamide] in cattle kidney tissue has been developed. The assay involves isolation of a drug-containing fraction by solvent extraction, methylation of the analyte, and fused-silica capillary column gas chromatography-negative-ion chemical-ionization mass spectrometry of the pentamethyl derivative of clorsulon. The intensities of four negative ions [m/z 406 and 408 (trichloro species) and m/z 413 and 415 (dichloro species)] are monitored. Confirmation of the presence of drug in an analyte requires that all four ions appear at the appropriate retention time with their intensity ratios within 10-15% of those arising from analysis of the reference standard, methylated clorsulon; the lower limit of detection is 3 ppb. Quantification of the drug is based on the intensity of the m/z 406 ion. Identification and quantification of residues by the gas chromatographic-mass spectrometric assay gave results in good agreement with those obtained with an electron-capture gas chromatographic assay. PMID:3654857

  17. [Determination of trifluralin residue in aquatic products and edible oils by gas chromatography-negative chemical ionization mass spectrometry].

    PubMed

    Wang, Li; Xia, Guanghui; Shen, Weijian; Wu, Bin; Zhang, Rui; Lu, Huiyuan; Shen, Chongyu; Zhao, Zengyun

    2014-03-01

    A confirmatory method was established for the determination of trifluralin residue in aquatic products and edible oils with the technique of offline disperse solid phase extraction and gas chromatography-negative chemical ionization mass spectrometry (DSPE-GC-MS/NCI). Trifluralin was extracted from aquatic products and edible oils with acetonitrile, and liquid-liquid partitioning formed by adding anhydrous magnesium sulfate followed by a simple cleanup step known as dispersive solid-phase extraction. The aliquot was analyzed by GC-MS/NCI using isotope internal standard method. The method was reliable and stable. The recoveries of trifluralin were in the range from 80% to 100% at three spiked levels of 1.0, 2.0, and 3.0 microg/kg, and the RSDs were not more than 10.3%. The linearity of method was good from 1 to 40 microg/L, and the LOD was 0.02 microg/kg. This method can be used as a conclusive evidence method for the determination of trifluralin residue in aquatic products and edible oils. PMID:24984475

  18. [Determination of four insecticide residues in honey and royal jelly by gas chromatography-negative chemical ionization mass spectrometry].

    PubMed

    Xia, Guanghui; Shen, Weijian; Yu, Keyao; Wu, Bin; Zhang, Rui; Shen, Chongyu; Zhao, Zengyun; Bian, Xiaohong; Xu, Jiyang

    2014-07-01

    A method was developed for the determination of four insecticide residues in honey and royal jelly by gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS). The honey and royal jelly samples were treated with different preparation methods as the result of the different components. The honey sample was extracted with ethyl acetate and cleaned up with primary second amine, and the royal jelly sample was extracted with acetonitrile-water (1:1, v/v), and cleaned up with a C18 solid-phase extraction column. Finally, the extracts of the honey and royal jelly were analyzed by GC-NCI/MS in selected ion monitoring (SIM) mode separately. External standard calibration method was used for quantification. The linearities of calibration curves of the four insecticides were good with the correlation coefficients greater than 0.99 in the range of 50-500 microg/L. The limits of the detection (LODs) of the four insecticides were in the range of 0.12- 5.0 microg/kg, and the limits of the quantification (LOQs) were in the range of 0.40-16.5 microg/kg. The recoveries of the four insecticides spiked in honey and royal jelly at three spiked levels (10, 15 and 20 microg/kg) were in the range of 78.2 -110.0%, and the relative standard deviations (RSDs) were all below 14%. The sensitivity and selectivity of this method were good with no interfering peaks. The proposed method is simple quick and effective to analyze the four insecticide residues in honey and royal jelly. PMID:25255567

  19. Determination of picogram levels of midazolam, and 1- and 4-hydroxymidazolam in human plasma by gas chromatography–negative chemical ionization–mass spectrometry

    Microsoft Academic Search

    C. B. Eap; G. Bouchoux; K. Powell Golay; P. Baumann

    2004-01-01

    Midazolam is a widely accepted probe for phenotyping cytochrome P4503A. A gas chromatography–mass spectrometry (GC–MS)–negative chemical ionization method is presented which allows measuring very low levels of midazolam (MID), 1-OH midazolam (1OHMID) and 4-OH midazolam (4OHMID), in plasma, after derivatization with the reagent N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide. The standard curves were linear over a working range of 20pg\\/ml to 5ng\\/ml for the three

  20. 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

  1. 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

  2. Confirmatory method for sulfonamide residues in animal tissues by gas chromatography and pulsed positive ion-negative ion-chemical ionization mass spectrometry.

    PubMed

    Mooser, A E; Koch, H

    1993-01-01

    A confirmatory method has been developed for determination of 13 sulfonamides in edible tissues. The assay involves extraction from a solution resulting from a screening procedure by liquid chromatography and subsequent derivatization. Sulfachloropyridazine (SCP), sulfadiazine (SDA), sulfadimethoxine (SDM), sulfamethazine (SMZ), sulfamerazine (SME), sulfamethoxazole (SMX), sulfamethoxypyridazine (SMP), sulfapyridine (SPR), sulfaquinoxaline (SQX), and sulfathiazole (STA) were detected as the N1-methyl-N4-trifluoroacetyl derivatives, sulfaguanidine (SGU) as the same derivative after cyclization by hexafluoroacetylacetone, and sulfacetamide (SAC) as the methyl derivative. These sulfonamides were detected by gas chromatography and pulsed positive ion-negative ion-chemical ionization mass spectrometry with methane as the reactant gas, whereas sulfanilamide (SAA) was determined as the methyl derivative by electron-impact ionization. PMID:8241826

  3. Structural determination of zinc dithiophosphates in lubricating oils by gas chromatography-mass spectrometry with electron impact and electron-capture negative ion chemical ionization.

    PubMed

    Becchi, M; Perret, F; Carraze, B; Beziau, J F; Michel, J P

    2001-01-01

    Pentafluorobenzyl ester derivatives were used to identify zinc dialkyldithiophosphates and diaryldithiophosphates antiwear engine oil additives by GC-electron impact ionization (EI) MS and GC-electron-capture negative ion chemical ionization (ECNCI) MS analysis. GC-EI-MS of the dialkyldithiophosphate-pentafluorobenzyl derivatives afforded characteristic fragment ions corresponding to the cleavage of one and two alkyl radicals. In most cases, information was only obtained on one alkyl chain. Additional and complete information was obtained with retention time indices using synthetic derivatives and with GC-ECNCI-MS analysis. ECNCI afforded characteristic dithiophosphate anions which allowed the determination of the total number of carbon atoms in the alkyl radicals. The diastereoisomer mixtures of 2-hydroxy-sec.-alkyl radicals were completely separated on GC analysis. PMID:11206788

  4. Tungsten isotope ratio determinations by negative thermal ionization mass spectrometry

    Microsoft Academic Search

    Joachim Völkening; Manfred Köppe; Klaus G. Heumann

    1991-01-01

    A precise determination of the isotopic abundances of tungsten with natural isotopic composition is presented. WO-3 ions are generated by negative thermal ionization (NTI) in a double-filament ion source. La2O3 is used as a chemical substance to reduce the electron work function of the rhenium filament material. An ionization efficiency of 1% is obtained for sample loadings of 100 ng.

  5. Comparison of negative-ion proton-transfer with iodide ion chemical ionization mass spectrometry for quantification of isocyanic acid in ambient air

    NASA Astrophysics Data System (ADS)

    Woodward-Massey, Robert; Taha, Youssef M.; Moussa, Samar G.; Osthoff, Hans D.

    2014-12-01

    Isocyanic acid (HNCO) is a trace gas pollutant of potential importance to human health whose measurement has recently become possible through the development of negative-ion proton-transfer chemical ionization mass spectrometry (NI-PT-CIMS) with acetate reagent ion. In this manuscript, an alternative ionization and detection scheme, in which HNCO is quantified by iodide CIMS (iCIMS) as a cluster ion at m/z 170, is described. The sensitivity was inversely proportional to water vapor concentration but could be made independent of humidity changes in the sampled air by humidifying the ion-molecule reaction (IMR) region of the CIMS. The performance of the two ionization schemes was compared and contrasted using ambient air measurements of HNCO mixing ratios in Calgary, AB, Canada, by NI-PT-CIMS with acetate reagent ion from Dec 16 to 20, 2013, and by the same CIMS operated in iCIMS mode from Feb 3 to 7, 2014. The iCIMS exhibited a greater signal-to-noise ratio than the NI-PT-CIMS, not because of its sensitivity, which was lower (?0.083 normalized counts per second (NCPS) per parts-per-trillion by volume (pptv) compared to ?9.7 NCPS pptv-1), but because of a much lower and more stable background (3 ± 4 compared to a range of ?2 × 103 to ?6 × 103 NCPS). For the Feb 2014 data set, the HNCO mixing ratios in Calgary air ranged from <12 to 94 pptv (median 34 pptv), were marginally higher at night than during day, and correlated with nitrogen oxide (NOx = NO + NO2) mixing ratios and submicron particle volume. The ratios of HNCO to NOx observed are within the range of emission ratios reported for gasoline-powered motor vehicles.

  6. 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

  7. Particle beam liquid chromatography/mass spectrometry with negative ion chemical ionization for the confirmation of ivermectin residue in bovine milk and liver.

    PubMed

    Heller, D N; Schenck, F J

    1993-03-01

    Particle beam liquid chromatography/mass spectrometry (LC/MS) using negative ion chemical ionization was applied to the analysis of ivermectin residue in bovine milk and liver. Samples were prepared by liquid/liquid extraction followed by alumina B solid-phase extraction clean-up. On-line LC/MS of extracts was carried out on a C-18 bonded silica column. Signals were observed from on-column injections of 4 ng dihydro-avermectin B1a (H2B1a) in extracts equivalent to 2 ml milk or 0.3 g liver. The specificity required for a regulatory confirmation procedure was achieved by monitoring the H2B1a molecular ion and four fragment ions. Ion chromatogram peak areas were at least three times greater than control samples integrated over the same time window. Coeluting matrix compounds enhanced the response and altered the abundance pattern of H2B1a. To compensate for this matrix effect, control milk extracts were spiked with H2B1a standard and used for the abundance matching for the abundance matching requirement of regulatory confirmation. PMID:8461342

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

    PubMed

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

    2003-02-01

    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 phase. Concentrations of eight to ten mononitro-PAHs and three dinitropyrenes were determined in three diesel particulate-related SRMs: SRM 1650a Diesel Particulate Matter, SRM 1975 Diesel Particulate Extract, and SRM 2975 Diesel Particulate Matter (Industrial Forklift). The results from GC/MS NICI using two different columns (5% phenyl methylpolysiloxane and 50% phenyl methylpolysiloxane) were compared to each other and to results from two other laboratories for selected nitro-PAHs. 1-Nitropyrene was the most abundant nitro-PAHs in each of the diesel particulate SRMs (19.8+/-1.1 micro g g(-1) particle in SRM 1650a and 33.1+/-0.6 micro g g(-1) particle in SRM 2975). Three dinitropyrene isomers were measured in SRM 1975 at 0.5-1.4 micro g g(-1) extract and in SRM 2975 at 1-3 micro g g(-1) particle. PMID:12589503

  9. [Determination of polybrominated diphenyl ethers in indoor dust using ultrasonic-assisted extraction and gas chromatography-negative chemical ionization mass spectrometry].

    PubMed

    Zhang, Xiaoling; Wang, Bingling; Lu, Xiaomei; Zhang, Qi; Zhang, Zhengdong

    2012-12-01

    A method for the determination of eight polybrominated diphenyl ethers (PBDEs) in indoor dust was developed. A vacuum cleaner was used for gathering the house dust, and n-hexane was added and the extraction was performed in an ultrasonic bath. The supernatant was concentrated and then n-hexane was added to 0.1 mL. Gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS) has been investigated for the determination of the eight PBDE congeners in indoor dust. The eight PBDEs were separated within 20 min. The absolute recoveries were 53.2% - 107.6%. The relative standard deviations (RSDs) of intra-day were between 2.8% and 16.5%, while the RSDs of inter-day were between 6.4% and 22.6%. The limits of detection (LOD, S/N = 3) were in the range of 0.003 - 0.015 ng/g except the LOD of BDE-209 was 0.15 ng/g. The results indicated that the proposed method is sensitive, accurate, fast, simple, low solvent consumption and suitable for the determination of tri- to deca-BDEs in indoor dust. PMID:23593880

  10. 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.

  11. Measurements of gas-phase inorganic and organic acids from biomass fires by negative-ion proton-transfer chemical-ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Veres, Patrick; Roberts, James M.; Burling, Ian R.; Warneke, Carsten; de Gouw, Joost; Yokelson, Robert J.

    2010-12-01

    Emissions from 34 laboratory biomass fires were investigated at the combustion facility of the U.S. Department of Agriculture Fire Sciences Laboratory in Missoula, Montana. Gas-phase organic and inorganic acids were quantified using negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), open-path Fourier transform infrared spectroscopy (OP-FTIR), and proton-transfer-reaction mass spectrometry (PTR-MS). NI-PT-CIMS is a novel technique that measures the mass-to-charge ratio (m/z) of ions generated from reactions of acetate (CH3C(O)O-) ions with inorganic and organic acids. The emission ratios for various important reactive acids with respect to CO were determined. Emission ratios for isocyanic acid (HNCO), 1,2 and 1,3-benzenediols (catechol, resorcinol), nitrous acid (HONO), acrylic acid, methacrylic acid, propionic acid, formic acid, pyruvic acid, and glycolic acid were measured from biomass burning. Our measurements show that there is a significant amount of HONO in fresh smoke. The NI-PT-CIMS measurements were validated by comparison with OP-FTIR measurements of HONO and formic acid (HCOOH) and with PTR-MS measurements of HCOOH.

  12. Ground based organic and inorganic acids measurements using negative-ion proton-transfer chemical-ionization mass spectrometry in Pasadena, CA during CalNex 2010

    NASA Astrophysics Data System (ADS)

    Veres, P. R.; Roberts, J. M.; Cochran, A. K.; Warneke, C.; de Gouw, J. A.

    2010-12-01

    Measurements of a variety of organic acids (e.g. formic acid, pyruvic acid, glycolic acid) and inorganic acids (HNCO, HONO, HCl, HBr, HNO3) were made using a novel negative-ion proton-transfer chemical ionization mass spectrometer (NI-PT-CIMS) deployed at a ground site in Pasadena, CA during May and June 2010 as part of CalNex 2010. In this presentation, a summary of the observations will be given. Organic acids exhibited strong diurnal trends peaking shortly after solar maximum. Mixing ratios of HNO3 peaked at 14 parts-per-billion by volume (ppbv) with HCl reaching as high as 8 ppbv during the measurement period. HNO3 and HCl were strongly correlated throughout the measurement period; however, slopes of the correlation plots widely varied both diurnally as well as within a given day. HONO was measured with nighttime levels often reaching as high as 3 ppbv. We also report data for isocyanic acid (HNCO) that is among the first quantitative measurements of this species in the ambient atmosphere.

  13. The determination of 5-hydroxytryptamine, related indolealkylamines and 5-hydroxyindoleacetic acid in the bovine eye by gas chromatography-negative ion chemical ionization mass spectrometry.

    PubMed

    Best, S A; Midgley, J M; Huang, W; Watson, D G

    1993-01-01

    Methods were developed for the analysis of 5-hydroxytryptamine, related indolealkylamines (tryptamine, melatonin, 5-methoxytryptamine, N-acetyl-5-hydroxytryptamine and 6-hydroxymelatonin) and 5-hydroxyindole-3-acetic acid (5HIAA) in bovine retina, aqueous and vitreous humours. 5-Hydroxytryptamine and related indolealkylamines were extracted and derivatized to form their corresponding pentafluoropropionyl spirocyclic derivatives. 5HIAA was extracted and derivatized to the corresponding pentafluoropropionamide-trifluoroethyl derivative. Identification and quantitation by gas chromatography-negative ion chemical ionization mass spectrometry was made with reference to deuteriated internal standards. 5-Hydroxytryptamine was present in all (n = 34) retinal samples analysed (20.53 +/- 1.64 ng) while N-acetyl-5-hydroxytryptamine was detected in half of the samples of retina (0.06 +/- 0.02 ng). Melatonin (0.15 +/- 0.06 ng) and tryptamine (0.78 +/- 0.34 ng) were detected in only a small number of retinas. 5-Methoxytryptamine was not present in retina. 5-Hydroxytryptamine was also present in aqueous (0.76 +/- 0.17 ng ml-1 and vitreous (0.35 +/- 0.05 ng ml-1' humours from bovine eye. Tryptamine, melatonin, 5-methoxytryptamine and N-acetyl-5-hydroxytryptamine were not detected in bovine aqueous and vitreous humours. 5HIAA was found in both bovine aqueous (2.03 +/- 0.38 ng ml-1) and vitreous (0.65 +/- 0.06 ng ml-1) humours, but its consistent determination in retina was obviated by interference from spurious peaks. PMID:7689343

  14. 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

  15. Gas phase enantiomeric distinction of (R)- and (S)-aromatic hydroxy esters by negative ion chemical ionization mass spectrometry using a chiral reagent gas

    NASA Astrophysics Data System (ADS)

    Mancel, Valérie; Sellier, Nicole; Lesage, Denis; Fournier, Françoise; Tabet, Jean-Claude

    2004-10-01

    Negative ion chemical ionization (NICI) using a chiral reagent gas such as (2S,3S) butanediol (GSS) allows the differentiation of chiral [alpha] hydroxy esters (MR or MS). The distinction is significantly enhanced by using CID on the deprotonated hetero dimer [M + (GSS-H)]-. The contribution of a non covalent [M + (GSS-H)]- competitive form is very minor. In fact, a covalent form appears favored. To produce a covalent adduct ion, an enantioselectivity of the alkoxide attack on the electrophilic ester site to form a tetravalent adduct is suggested by the product ion abundances. This observed steric control is consistent with the one observed in solution (Cram-Felkin addition/reduction orientation). The dissociations under collision conditions of the product deprotonated diastereomeric compounds show a stereospecific effect in the elimination of alcohol from the tetravalent adduct ions rather than a regeneration of the deprotonated diol reagent as expected from non-covalent heterodimer. This study shows an orientation with a chiral compound that allows, from an analytical point of view, the distinction of enantiomers and the attribution of chirality in the gas phase under NICI conditions.

  16. Mechanism of branching in negative ionization fronts.

    PubMed

    Arrayás, Manuel; Fontelos, Marco A; Trueba, José L

    2005-10-14

    When a strong electric field is applied to nonconducting matter, narrow channels of plasma called streamers may form. Branchlike patterns of streamers have been observed in anode directed discharges. We explain a mechanism for branching as the result of a balance between the destabilizing effect of impact ionization and the stabilizing effect of electron diffusion on ionization fronts. The dispersion relation for transversal perturbation of a planar negative front is obtained analytically when the ratio D between the electron diffusion coefficient and the intensity of the externally imposed electric field is small. We estimate the spacing lambda between streamers and deduce a scaling law lambda approximately D(1/3). PMID:16241810

  17. Ionization phenomena and sources of negative ions

    SciTech Connect

    Alton, G.D.

    1983-01-01

    Negative ion source technology has rapidly advanced during the past several years as a direct consequence of the discovery of Krohn that negative ion yields can be greatly enhanced by sputtering in the presence of Group IA elements. Today, most negative ion sources use this discovery directly or the principles implied to effect negative ion formation through surface ionization. As a consequence, the more traditional direct extraction plasma and charge exchange sources are being used less frequently. However, the charge exchange generation mechanism appears to be as universal, is very competitive in terms of efficiency and has the advantage in terms of metastable ion formation. In this review, an attempt has been made to briefly describe the principal processes involved in negative ion formation and sources which are representative of a particular principle. The reader is referred to the literature for specific details concerning the operational characteristics, emittances, brightnesses, species and intensity capabilities of particular sources. 100 references.

  18. Determination of picogram levels of midazolam, and 1- and 4-hydroxymidazolam in human plasma by gas chromatography-negative chemical ionization-mass spectrometry.

    PubMed

    Eap, C B; Bouchoux, G; Powell Golay, K; Baumann, P

    2004-04-01

    Midazolam is a widely accepted probe for phenotyping cytochrome P4503A. A gas chromatography-mass spectrometry (GC-MS)-negative chemical ionization method is presented which allows measuring very low levels of midazolam (MID), 1-OH midazolam (1OHMID) and 4-OH midazolam (4OHMID), in plasma, after derivatization with the reagent N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide. The standard curves were linear over a working range of 20 pg/ml to 5 ng/ml for the three compounds, with the mean coefficients of correlation of the calibration curves (n = 6) being 0.999 for MID and 1OHMID, and 1.0 for 4OHMID. The mean recoveries measured at 100 pg/ml, 500 pg/ml, and 2 ng/ml, ranged from 76 to 87% for MID, from 76 to 99% for 1OHMID, from 68 to 84% for 4OHMID, and from 82 to 109% for N-ethyloxazepam (internal standard). Intra- (n = 7) and inter-day (n = 8) coefficients of variation determined at three concentrations ranged from 1 to 8% for MID, from 2 to 13% for 1OHMID and from 1 to 14% for 4OHMID. The percent theoretical concentrations (accuracy) were within +/-8% for MID and 1OHMID, within +/-9% for 4OHMID at 500 pg/ml and 2 ng/ml, and within +/-28% for 4OHMID at 100 pg/ml. The limits of quantitation were found to be 10 pg/ml for the three compounds. This method can be used for phenotyping cytochrome P4503A in humans following the administration of a very low oral dose of midazolam (75 microg), without central nervous system side-effects. PMID:15018796

  19. 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

  20. 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

  1. A multi-residue method for pesticides analysis in green coffee beans using gas chromatography-negative chemical ionization mass spectrometry in selective ion monitoring mode.

    PubMed

    Pizzutti, Ionara R; de Kok, Andre; Dickow Cardoso, Carmem; Reichert, Bárbara; de Kroon, Marijke; Wind, Wouter; Weber Righi, Laís; Caiel da Silva, Rosselei

    2012-08-17

    In this study, a new gas chromatography-mass spectrometry (GC-MS) method, using the very selective negative chemical ionization (NCI) mode, was developed and applied in combination with a modified acetonitrile-based extraction method (QuEChERS) for the analysis of a large number of pesticide residues (51 pesticides, including isomers and degradation products) in green coffee beans. A previously developed integrated sample homogenization and extraction method for both pesticides and mycotoxins analysis was used. An homogeneous slurry of green milled coffee beans and water (ratio 1:4, w/w) was prepared and extracted with acetonitrile/acetic acid (1%), followed by magnesium sulfate addition for phase separation. Aliquots from this extract could be used directly for LC-MS/MS analysis of mycotoxins and LC-amenable pesticides. For GC-MS analysis, a further clean-up was necessary. C18- and PSA-bonded silica were tested as dispersive solid-phase extraction (d-SPE) sorbents, separate and as a mixture, and the best results were obtained using C18-bonded silica. For the optimal sensitivity and selectivity, GC-MS detection in the NCI-selected ion monitoring (SIM) mode had to be used to allow the fast analysis of the difficult coffee bean matrix. The validation was performed by analyzing recovery samples at three different spike concentrations, 10, 20 and 50 ?g kg(-1), with 6 replicates (n=6) at each concentration. Linearity (r(2)) of calibration curves, estimated instrument and method limits of detection and limits of quantification (LOD(i), LOD(m), LOQ(i) and LOQ(m), respectively), accuracy (as recovery %), precision (as RSD%) and matrix effects (%) were determined for each individual pesticide. From the 51 analytes (42 parent pesticides, 4 isomers and 5 degradation products) determined by GC-MS (NCI-SIM), approximately 76% showed average recoveries between 70-120% and 75% and RSD ? 20% at the lowest spike concentration of 10 ?g kg(-1), the target method LOQ. For the spike concentrations of 20 and 50 ?g kg(-1), the recoveries and RSDs were even better. The validated LOQ(m) was 10, 20 and 50 ?g kg(-1) for respectively 33, 3 and 6 of the analytes studied. For five compounds, the European Union method performance requirements for the validation of a quantitative method (average recoveries between 70-120% and repeatability RSD ? 20%) were not achieved and 4 problematic pesticides (captan, captafol, folpet and dicofol) could not be detected as their parent compound, but only via their degradation products. Although the matrix effect (matrix-enhanced detector response) was high for all pesticides studied, the matrix interference was minimal, due to the high selectivity obtained with the GC-NCI-MS detection. Matrix-matched calibration for applying the method in routine analysis is recommended for reliable quantitative results. PMID:22771261

  2. Sensitive, rapid and validated gas chromatography\\/negative ion chemical ionization-mass spectrometry assay including derivatisation with a novel chiral agent for the enantioselective quantification of amphetamine-type stimulants in hair

    Microsoft Academic Search

    Liliane Ferreira Martins; Michel Yegles; Heesun Chung; Robert Wennig

    2006-01-01

    A novel chiral derivatisation agent, (2S,4R)-N-heptafluorobutyryl-4-heptafluorobutoyloxy-prolyl chloride, was used for the indirect resolution of amphetamine (AM), methamphetamine (MA), 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA) and 3,4-methylenedioxyethylamphetamine (MDEA) enantiomers using gas chromatography coupled to mass spectrometry operating in the negative-ion chemical ionization mode (GC\\/MS-NICI). This new chiral derivatisation reagent was readily obtained in optically pure form after a simple two-step synthesis. Optimal derivatisation

  3. Development and validation of an analytical method for determination of 3-chloropropane-1,2-diol in rat blood and urine by gas chromatography-mass spectrometry in negative chemical ionization mode.

    PubMed

    Berger-Preiss, Edith; Gerling, Susanne; Apel, Elisabeth; Lampen, Alfonso; Creutzenberg, Otto

    2010-09-01

    We have developed a highly selective and sensitive method using gas chromatography-mass spectrometry with negative chemical ionization for measuring 3-chloropropane-1,2-diol (3-MCPD) in rat blood and urine. Samples were adsorbed on silica gel, extracted with ethyl acetate, and derivatized by chemical derivatization with heptafluorobutyric acid anhydride. For quantification, matrix-based calibration curves and 3-MCPD-d (5), as an isotope-labeled internal standard, were used. The relative recoveries of 3-MCPD were between 80 and 110% in most cases and the relative standard deviations were typically less than 10%, with some exceptions. The limit of quantification of the method was found to be about 2 ng/mL. In conclusion, a valuable, robust, and sensitive method for detection of 3-MCPD is now available for biokinetics studies. PMID:20640896

  4. USE OF NEGATIVE ARI IONIZATION FOR REDUCING BACTERIAL PATHOGENS AND SPORES ON STAINLESS STEEL SURFACES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The use of chemicals in food plant sanitation for removing and killing microorganisms could be reduced by the use of alternative non-chemical interventions. Negative air ionization is a new technology that has shown potential to effectively reduce airborne and surface microorganisms. Current studies...

  5. Chemical form effects on the surface ionization of lithium halides

    Microsoft Academic Search

    Tatsuya Suzuki; Hideki Iwabuchi; Kazuko Takahashi; Masao Nomura; Makoto Okamoto; Yasuhiko Fujii

    1995-01-01

    The surface ionization of lithium halides, i.e. fluoride, chloride, bromide and iodide, was studied using a mass spectrometer. In the measurements of ionization using rhenium filaments, it was found that the ionization efficiencies depend on the chemical forms of the samples. To analyze the mechanism of ionization, direct ionization by dissociative ionization is introduced in the present work. The ionization

  6. Development of negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) for the measurement of gas-phase organic acids in the atmosphere

    NASA Astrophysics Data System (ADS)

    Veres, Patrick; Roberts, James M.; Warneke, Carsten; Welsh-Bon, Daniel; Zahniser, Mark; Herndon, Scott; Fall, Ray; de Gouw, Joost

    2008-07-01

    We have developed a negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) technique for on-line analysis of gaseous organic and inorganic acids. In this detection scheme, acetate ions (CH3C(O)O-) react very selectively with atmospheric trace acids, by proton transfer, to produce unique product ion species. We tested this ion chemistry for 11 species of which only four showed measurable fragmentation. We investigated both the time response of the inlet and humidity dependence for both formic acid and pyruvic acid measurements. A formic acid calibration was performed and found a sensitivity of 21 ± 4.3 counts per second per pptv. Formic acid measurements made during two separate informal ambient air intercomparisons: (1) with a quantum cascade IR laser absorption system (QCL) and (2) a proton-transfer reaction mass spectrometer (PTR-MS) show good agreement validating this measurement technique. The measurements of the NI-PT-CIMS and PTR-MS agree to within 5% with a high degree of correlation (r2 > 0.93). We have found the NI-PT-CIMS detection limit for formic acid is approximately 80-90 pptv for a 1 s integration period, and is currently limited by the formate background in the instrument. The fast time response and high sensitivity of the NI-PT-CIMS method make it a promising technique for the measurement of organic acids in ambient conditions.

  7. 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

  8. Simultaneous detection of stable isotope-labeled and unlabeled L-tryptophan and of its main metabolites, L-kynurenine, serotonin and quinolinic acid, by gas chromatography/negative ion chemical ionization mass spectrometry.

    PubMed

    Sano, Mitsue; Ferchaud-Roucher, Véronique; Nael, Charlotte; Aguesse, Audrey; Poupeau, Guillaume; Castellano, Blandine; Darmaun, Dominique

    2014-02-01

    A method for the detection of unlabeled and (15)N2 -labeled L-tryptophan (L-Trp), L-kynurenine (L-Kyn), serotonin (5-HT) and quinolinic acid (QA) in human and rat plasma by GC/MS is described. Labeled and unlabeled versions of these four products were analyzed as their acyl substitution derivatives using pentafluoropropionic anhydride and 2,2,3,3,3-pentafluoro-1-propanol. Products were then separated by GC and analyzed by selected ion monitoring using negative ion chemical ionization mass spectrometry. L-[(13)C11, (15)N2]-Trp, methyl-serotonin and 3,5-pyridinedicarboxylic acid were used as internal standards for this method. The coefficients of variation for inter-assay repeatability were found to be approximately 5.2% for L-Trp and (15)N2-Trp, 17.1% for L-Kyn, 16.9% for 5-HT and 5.8% for QA (n?=?2). We used this method to determine isotope enrichments in plasma L-Trp over the course of a continuous, intravenous infusion of L-[(15) N2 ]Trp in pregnant rat in the fasting state. Plasma (15)N2-Trp enrichment reached a plateau at 120?min. The free Trp appearance rate (Ra) into plasma was 49.5?±?3.35?µmol/kg/h. The GC/MS method was applied to determine the enrichment of (15)N-labeled L-Trp, L-Kyn, 5-HT and QA concurrently with the concentration of non-labeled L-Trp, L-Kyn, 5-HT and QA in plasma. This method may help improve our understanding on L-Trp metabolism in vivo in animals and humans and potentially reveal the relative contribution of the four pathways of L-Trp metabolism. PMID:24677305

  9. Development of Ion Drift-Chemical Ionization Mass Spectrometry

    E-print Network

    Development of Ion Drift-Chemical Ionization Mass Spectrometry Edward C. Fortner, Jun Zhao An ion drift-chemical ionization mass spectrometry (ID- CIMS) technique has been developed to detect in laboratory kinetic investigations and field measurements. Chemical ionization mass spectrometry (CIMS) has

  10. Chemical protection against ionizing radiation. Final report

    SciTech Connect

    Livesey, J.C.; Reed, D.J.; Adamson, L.F.

    1984-08-01

    The scientific literature on radiation-protective drugs is reviewed. Emphasis is placed on the mechanisms involved in determining the sensitivity of biological material to ionizing radiation and mechanisms of chemical radioprotection. In Section I, the types of radiation are described and the effects of ionizing radiation on biological systems are reviewed. The effects of ionizing radiation are briefly contrasted with the effects of non-ionizing radiation. Section II reviews the contributions of various natural factors which influence the inherent radiosensitivity of biological systems. Inlcuded in the list of these factors are water, oxygen, thiols, vitamins and antioxidants. Brief attention is given to the model describing competition between oxygen and natural radioprotective substances (principally, thiols) in determining the net cellular radiosensitivity. Several theories of the mechanism(s) of action of radioprotective drugs are described in Section III. These mechanisms include the production of hypoxia, detoxication of radiochemical reactive species, stabilization of the radiobiological target and the enhancement of damage repair processes. Section IV describes the current strategies for the treatment of radiation injury. Likely areas in which fruitful research might be performed are described in Section V. 495 references.

  11. Charge transfer effects in molecule-negative ion complexes induced by core ionization

    NASA Astrophysics Data System (ADS)

    Streltsov, A. I.; Dobrodey, N. V.; Cederbaum, L. S.

    2003-08-01

    A variety of charge transfer effects can take place as a result of core ionization of anion-molecule complexes. As specific examples we study the core ionization of Na-H2O and Cl-H2O clusters using an ab initio Green's function method. The site-localized character of the electron distribution in the ground state of these weakly bound clusters favors a transfer of an electron from the negative atomic ion to the H2O molecular unit upon ionization of the O1s core level. The charge transferred screens the created core hole giving rise to the appearance of low-lying satellites which are completely absent in the spectrum of the isolated H2O molecule. Energies and intensities of the charge-transfer satellites are found to depend strongly on the chemical type of the atomic anion. While the bandshape of the O1s-1 spectrum of Cl-H2O is very similar to that of isolated H2O, the spectrum of Na-H2O has virtually nothing to do with the core-ionization spectrum of the water molecule. Interestingly, the charge-transfer satellites seen in the O1s core-ionization spectrum of the Cl-H2O cluster can be well related to states in the O1s core-excitation spectrum of the isolated H2O molecule. The physics of core ionization of the clusters is discussed in detail.

  12. 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...

  13. 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.

  14. LETTER TO THE EDITOR: Double ionization of atomic negative ions in an intense laser field

    Microsoft Academic Search

    J. B. Greenwood; G. F. Collins; J. Pedregosa-Gutierrez; J. McKenna; A. Murphy; J. T. Costello

    2003-01-01

    In recent years there have been many studies of multiple ionization of closed shell rare gas atoms by intense laser fields. Until now no similar work has been done in the study of more diverse targets such as negative ions where low binding energies and strong electron correlations could yield distinctive behaviour. We present the first results of ionization of

  15. Plasma-assisted reaction chemical ionization for elemental mass spectrometry of organohalogens.

    PubMed

    Wang, Haopeng; Lin, Ninghang; Kahen, Kaveh; Badiei, Hamid; Jorabchi, Kaveh

    2014-04-01

    We present plasma-assisted reaction chemical ionization (PARCI) for elemental analysis of halogens in organic compounds. Organohalogens are broken down to simple halogen-containing molecules (e.g., HBr) in a helium microwave-induced plasma followed by negative mode chemical ionization (CI) in the afterglow region. The reagent ions for CI originate from penning ionization of gases (e.g., N2) introduced into the afterglow region. The performance of PARCI-mass spectrometry (MS) is evaluated using flow injection analyses of organobromines, demonstrating 5-8 times better sensitivities compared with inductively coupled plasma MS. We show that compound-dependent sensitivities in PARCI-MS mainly arise from sample introduction biases. PMID:24474553

  16. Negative Temperature Coefficient in Chemical Reactions

    Microsoft Academic Search

    I A Leenson; Gleb B Sergeev

    1984-01-01

    A systematic analysis of reactions whose rate decreases with increase of temperature is presented. The possibility of a negative temperature coefficient in the elementary reactions is examined from the standpoint of the transition state theory and of collision theory. The mechanisms of complex reactions in which the temperature dependence of the rate is anomalous are discussed, and possible reasons for

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

    Microsoft Academic Search

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

    2009-01-01

    Utilizing synchronized dual-polarity matrix-assisted laser desorption\\/ionization (MALDI) mass spectrometry, we found good\\u000a evidence of the incoherent production of positive and negative matrix ions. Using thin, homogeneous 2,5-dehydroxybenzoic acid\\u000a (DHB) matrix films, positive and negative matrix ions were found to appear at different threshold laser fluences. The presence\\u000a of molecular matrix ions of single charge polarity suggests that the existence of

  18. Attempts at Aerosol Control in a Turkey Rearing Confinement with Negative Air Ionization

    Microsoft Academic Search

    S. PARKER; H. BEAULIEU; D. PACHECO

    1983-01-01

    Aerosol control is a significant problem in agriculture and industry. Two separate studies were conducted to determine the effectiveness of a “negative air ionization” system in aerosol control. The first study was conducted with a turkey “brooder” barn and a control for a six-week period. The second study was conducted with a turkey “grow-out” barn and a control for a

  19. Self-consistent chemical model of partially ionized plasmas.

    PubMed

    Arkhipov, Yu V; Baimbetov, F B; Davletov, A E

    2011-01-01

    A simple renormalization theory of plasma particle interactions is proposed. It primarily stems from generic properties of equilibrium distribution functions and allows one to obtain the so-called generalized Poisson-Boltzmann equation for an effective interaction potential of two chosen particles in the presence of a third one. The same equation is then strictly derived from the Bogolyubov-Born-Green-Kirkwood-Yvon (BBGKY) hierarchy for equilibrium distribution functions in the pair correlation approximation. This enables one to construct a self-consistent chemical model of partially ionized plasmas, correctly accounting for the close interrelation of charged and neutral components thereof. Minimization of the system free energy provides ionization equilibrium and, thus, permits one to study the plasma composition in a wide range of its parameters. Unlike standard chemical models, the proposed one allows one to study the system correlation functions and thereby to obtain an equation of state which agrees well with exact results of quantum-mechanical activity expansions. It is shown that the plasma and neutral components are strongly interrelated, which results in the short-range order formation in the corresponding subsystem. The mathematical form of the results obtained enables one to both firmly establish this fact and to determine a characteristic length of the structure formation. Since the cornerstone of the proposed self-consistent chemical model of partially ionized plasmas is an effective pairwise interaction potential, it immediately provides quite an efficient calculation scheme not only for thermodynamical functions but for transport coefficients as well. PMID:21405782

  20. 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

  1. 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.

  2. 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).

  3. 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.

  4. Upper-Room Ultraviolet Light and Negative Air Ionization to Prevent Tuberculosis Transmission

    Microsoft Academic Search

    A. Roderick Escombe; David A. J Moore; Robert H Gilman; Marcos Navincopa; Eduardo Ticona; Bailey Mitchell; Catherine Noakes; Carlos Martínez; Patricia Sheen; Rocio Ramirez; Willi Quino; Armando Gonzalez; Jon S Friedland; Carlton A Evans

    2009-01-01

    BackgroundInstitutional tuberculosis (TB) transmission is an important public health problem highlighted by the HIV\\/AIDS pandemic and the emergence of multidrug- and extensively drug-resistant TB. Effective TB infection control measures are urgently needed. We evaluated the efficacy of upper-room ultraviolet (UV) lights and negative air ionization for preventing airborne TB transmission using a guinea pig air-sampling model to measure the TB

  5. Positive and Negative Self-Surface Ionization of Tungsten and Rhenium

    Microsoft Academic Search

    Milton D. Scheer; Joseph Fine

    1967-01-01

    The self-surface ionization of tungsten and rhenium has been investigated with a specially designed mass spectrometer. It has been found that both positive and negative singly charged atomic ions sublime from these metal surfaces in the 1900°—2600°K temperature range. The assumption that these processes can be described by a generalized Saha—Langmuir equation has been shown to be valid. The energies

  6. 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.

  7. The Chemical and Ionization Conditions in Weak Mg II Absorbers

    E-print Network

    Anand Narayanan; Jane C. Charlton; Toru Misawa; Rebecca E. Green; Tae-Sun Kim

    2008-08-19

    We present an analysis of the chemical and ionization conditions in a sample of 100 weak Mg II absorbers identified in the VLT/UVES archive of quasar spectra. Using a host of low ionization lines associated with each absorber in this sample, and on the basis of ionization models, we infer that the metallicity in a significant fraction of weak Mg II clouds is constrained to values of solar or higher, if they are sub-Lyman limit systems. Based on the observed constraints, we present a physical picture in which weak Mg II absorbers are predominantly tracing two different astrophysical processes/structures. A significant population of weak Mg II clouds, those in which N(Fe II) is much less than N(Mg II), identified at both low (z ~ 1) and high (z ~ 2) redshift, are potentially tracing gas in the extended halos of galaxies, analogous to the Galactic high velocity clouds. These absorbers might correspond to alpha-enhanced interstellar gas expelled from star-forming galaxies, in correlated supernova events. On the other hand, N(FeII) approximately equal to N(Mg II) clouds, which are prevalent only at lower redshifts (z < 1.5), must be tracing Type Ia enriched gas in small, high metallicity pockets in dwarf galaxies, tidal debris, or other intergalactic structures.

  8. Application of Ni-63 photo and corona discharge ionization for the analysis of chemical warfare agents and toxic wastes

    NASA Technical Reports Server (NTRS)

    Stach, J.; Adler, J.; Brodacki, M.; Doring, H.-R.

    1995-01-01

    Over the past decade, advances in instrumental design and refinements in the understanding of ion molecule reactions at atmospheric pressure enabled the application of Ion Mobility Spectrometry (IMS) as a simple inexpensive and sensitive analytical method for the detection of organic trace compounds. Positive and negative gas-phase ions for ion mobility spectrometry have been produced by a variety of methods, including photo-ionization, laser multi photon ionization, surface ionization, corona discharge ionization. The most common ion source used in ion mobility spectrometry is a radioactive Ni-63 foil which is favored due to simplicity, stability, convenience, and high selectivity. If reactant ions like (H2O(n)H)(+) or (H2O(n)O2)(-) dominate in the reaction region, nearly all kinds of compounds with a given proton or electron affinity; are ionized. However, the radioactivity of the Ni-63 foil is one disadvantage of this ion source that stimulates the development and application of other ionization techniques. In this paper, we report analyses of old chemical warfare agents and toxic wastes using Bruker RAID ion mobility spectrometers. Due to the modular construction of the measuring cell, the spectrometers can be equipped with different ion sources. The combined use of Ni-63, photo- and corona discharge ionization allows the identification of different classes of chemical compounds and yields in most cases comparable results.

  9. Methods for estimating the bioconcentration factor of ionizable organic chemicals.

    PubMed

    Fu, Wenjing; Franco, Antonio; Trapp, Stefan

    2009-07-01

    The bioaccumulation potential is an important criterion in risk assessment of chemicals. Several regressions between bioconcentration factor (BCF) in fish and octanol-water partition coefficient (K(OW)) have been developed for neutral organic compounds, but very few approaches address the BCF of ionizable compounds. A database with BCFs of 73 acids and 65 bases was collected from the literature. The BCF estimation method recommended by the Technical Guidance Document (TGD) for chemical risk assessment in the European Union was tested for ionizing substances using log K(OW) (corrected for the neutral species, log[ f(n) x K(OW)]) and log D (sum of log K(OW) of neutral and ionic molecule, apparent log K(OW)) as predictors. In addition, the method of Meylan et al. (Environ Toxicol Chem 1999; 18:664-672) for ionizable compounds and a dynamic cell model based on the Fick- Nernst-Planck equation were tested. Moreover, our own regressions for the BCF were established from log K(OW) and pK(a). The bioaccumulation of lipophilic compounds depends mainly on their lipophilicity, and the best predictor is log D. Dissociation, the pH-dependent ion trap, and electrical attraction of cations impact the BCF. Several methods showed acceptable results. The TGD regressions gave good predictions when log( f(n) x K(OW)) or log D were used as a predictor instead of log K(OW). The new regressions to log K(OW) and pK(a) performed similarly, with mean errors of approximately 0.4. The method of Meylan et al. did not perform as well. The cell model showed weak results for acids but was among the best methods for bases. PMID:19245273

  10. Upper-Room Ultraviolet Light and Negative Air Ionization to Prevent Tuberculosis Transmission

    PubMed Central

    Escombe, A. Roderick; Moore, David A. J; Gilman, Robert H; Navincopa, Marcos; Ticona, Eduardo; Mitchell, Bailey; Noakes, Catherine; Martínez, Carlos; Sheen, Patricia; Ramirez, Rocio; Quino, Willi; Gonzalez, Armando; Friedland, Jon S; Evans, Carlton A

    2009-01-01

    Background Institutional tuberculosis (TB) transmission is an important public health problem highlighted by the HIV/AIDS pandemic and the emergence of multidrug- and extensively drug-resistant TB. Effective TB infection control measures are urgently needed. We evaluated the efficacy of upper-room ultraviolet (UV) lights and negative air ionization for preventing airborne TB transmission using a guinea pig air-sampling model to measure the TB infectiousness of ward air. Methods and Findings For 535 consecutive days, exhaust air from an HIV-TB ward in Lima, Perú, was passed through three guinea pig air-sampling enclosures each housing approximately 150 guinea pigs, using a 2-d cycle. On UV-off days, ward air passed in parallel through a control animal enclosure and a similar enclosure containing negative ionizers. On UV-on days, UV lights and mixing fans were turned on in the ward, and a third animal enclosure alone received ward air. TB infection in guinea pigs was defined by monthly tuberculin skin tests. All guinea pigs underwent autopsy to test for TB disease, defined by characteristic autopsy changes or by the culture of Mycobacterium tuberculosis from organs. 35% (106/304) of guinea pigs in the control group developed TB infection, and this was reduced to 14% (43/303) by ionizers, and to 9.5% (29/307) by UV lights (both p < 0.0001 compared with the control group). TB disease was confirmed in 8.6% (26/304) of control group animals, and this was reduced to 4.3% (13/303) by ionizers, and to 3.6% (11/307) by UV lights (both p < 0.03 compared with the control group). Time-to-event analysis demonstrated that TB infection was prevented by ionizers (log-rank 27; p < 0.0001) and by UV lights (log-rank 46; p < 0.0001). Time-to-event analysis also demonstrated that TB disease was prevented by ionizers (log-rank 3.7; p = 0.055) and by UV lights (log-rank 5.4; p = 0.02). An alternative analysis using an airborne infection model demonstrated that ionizers prevented 60% of TB infection and 51% of TB disease, and that UV lights prevented 70% of TB infection and 54% of TB disease. In all analysis strategies, UV lights tended to be more protective than ionizers. Conclusions Upper-room UV lights and negative air ionization each prevented most airborne TB transmission detectable by guinea pig air sampling. Provided there is adequate mixing of room air, upper-room UV light is an effective, low-cost intervention for use in TB infection control in high-risk clinical settings. PMID:19296717

  11. Negative thermal ionization mass spectrometry of main group elements Part 2. 6th group: sulfur, selenium and tellurium

    Microsoft Academic Search

    M. Wachsmann; K. G. Heumann

    1992-01-01

    A systematic investigation of the formation of negative ions for the 6th main group elements using negative thermal ionization mass spectrometry (NTI-MS) is presented. A double-filament ion source with BaO on the ionization filament has been applied to reduce the work function of the rhenium filament material. S[radical sign]-, Se[radical sign]- and Te[radical sign]- were produced as most abundant ions.

  12. Gas chromatography plasma-assisted reaction chemical ionization mass spectrometry for quantitative detection of bromine in organic compounds.

    PubMed

    Lin, Ninghang; Wang, Haopeng; Kahen, Kaveh; Badiei, Hamid; Jorabchi, Kaveh

    2014-08-01

    We have recently introduced plasma-assisted reaction chemical ionization mass spectrometry (PARCI-MS) for elemental analysis of halogens in organic compounds. Here, we utilize gas chromatography (GC) coupled to PARCI-MS to investigate the mechanism of Br(-) ion generation from organobromines and to evaluate analytical performance of PARCI for organobromine analysis. Bromine atoms in compounds eluting from GC are converted to HBr in a low-pressure microwave induced helium plasma with trace amounts of hydrogen added as a reaction gas. Ionization is achieved by introducing nitrogen into the afterglow region of the plasma, liberating electrons via penning ionization and leading to formation of negative ions. We demonstrate that N2 largely affects the ionization process, whereas H2 affects both the ionization process and in-plasma reactions. Our investigations also suggest that dissociative electron capture is the main ionization route for formation of Br(-) ions. Importantly, GC-PARCI-MS shows a uniform response factor for bromine across brominated compounds of drastically different chemical structures, confirming PARCI's ability to quantify organobromines in the absence of compound-specific standards. Over 3 orders of magnitude linear dynamic range is demonstrated for bromine quantification. We report a detection limit of 29 fg of bromine on-column, ~4-fold better than inductively coupled plasma-MS. PMID:25003497

  13. 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.

  14. Evidence of Negative-Index Refraction in Nonlinear Chemical Waves

    NASA Astrophysics Data System (ADS)

    Yuan, Xujin; Wang, Hongli; Ouyang, Qi

    2011-05-01

    The negative index of refraction of nonlinear chemical waves has become a recent focus in nonlinear dynamics researches. Theoretical analysis and computer simulations have predicted that the negative index of refraction can occur on the interface between antiwaves and normal waves in a reaction-diffusion (RD) system. However, no experimental evidence has been found so far. In this Letter, we report our experimental design in searching for such a phenomenon in a chlorite-iodide-malonic acid (CIMA) reaction. Our experimental results demonstrate that competition between waves and antiwaves at their interface determines the fate of the wave interaction. The negative index of refraction was only observed when the oscillation frequency of a normal wave is significantly smaller than that of the antiwave. All experimental results were supported by simulations using the Lengyel-Epstein RD model which describes the CIMA reaction-diffusion system.

  15. 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).

  16. Analysis of Genetically Modified Canola Varieties by Atmospheric Pressure Chemical Ionization Mass Spectrometric and Flame Ionization Detection

    Microsoft Academic Search

    William C. Byrdwell; William E. Neff

    1996-01-01

    Canola oil triacylglycerols from genetically modified canola lines were conclusively identified by reverse phase HPLC coupled with atmospheric pressure chemical ionization mass spectrometric (APCI-MS) detection. APCI-MS is a soft ionization technique, which gave simple spectra for triacylglycerols. Spectral identification of the triacylglycerols was based on the diacylglycerol fragments and on the protonated molecular ion [M+H], except trisaturates which gave no

  17. Hydrogenation of unsaturated fatty esters during isobutane chemical ionization mass spectrometry

    Microsoft Academic Search

    William K. Rohwedder; Sandra M. Cox

    1984-01-01

    Hydrogenation of double bonds was observed to occur during the isobutane chemical ionization mass spectrometry (MS) of unsaturated\\u000a fatty esters. Chemical ionization (CI) spectra of a series of methyl esters in the C16–C20 carbon range containing 0–4 double\\u000a bonds showed a variety of ionization characteristics in the molecular ion cluster, including hydride abstraction, charge exchange,\\u000a protonation and, for the unsaturated

  18. Ammonia chemical ionization tandem mass spectrometry in structural determination of alkaloids.

    E-print Network

    Ammonia chemical ionization tandem mass spectrometry in structural determination of alkaloids. II 7 June 2001 Chemical ionization tandem mass spectrometry (CI-MS/MS) of alkaloids with ammonia alkaloids in extracts from six pseudomyrmecine ants of the genus Tetraponera. The MS/MS techniques along

  19. Peroxy radical observations using chemical ionization mass spectrometry during TOPSE

    NASA Astrophysics Data System (ADS)

    Cantrell, Christopher A.; Edwards, G. D.; Stephens, S.; Mauldin, L.; Kosciuch, E.; Zondlo, M.; Eisele, F.

    2003-03-01

    Peroxy radicals (HO2 + RO2) were measured by chemical conversion-chemical ionization mass spectroscopy in the TOPSE (Tropospheric Ozone Production about the Spring Equinox) campaign that took place February through May 2000. Instrumentation for these measurements was deployed on the NCAR/NSF C-130 aircraft that flew at latitudes from 40 to 85°N, and altitudes from the surface to 7.5 km over the North American continent. The measurements demonstrate the evolution of photochemical activity as time progresses through the study period due to increases in free radical source rates. The increase in average peroxy radical concentration moves northward as the maximum solar elevation and length of sunlit days increase. HOxROx (HO2 + RO2) concentrations are distributed lognormally with means of 11.5 and 7.8 pptv for the middle-latitude band (MLB) and high-latitude band (HLB), respectively. The observations agree well on average with steady state derived concentrations; measurement-model concentration ratios are 1.04 (MLB) and 0.94 (HLB). Concentrations within a given latitude band and altitude region sometimes appear to increase with NOx concentrations, but this correlation nearly disappears at low and moderate NOx levels when the data are parsed by radical production rate; lower radical levels are observed at the highest NOx levels measured (near 1 ppbv). These data are compared with results from other recent observations utilizing a variety of platforms.

  20. Cluster chemical ionization and deuterium exchange mass spectrometry in supersonic molecular Beams

    Microsoft Academic Search

    Shai Dagan; Aviv Amirav

    1996-01-01

    A cluster-based chemical ionization method has been developed that produces protonated molecular ions from molecules introduced\\u000a through a supersonic molecular beam interface. Mixed clusters of the analyte and a clustering agent (water or methanol) are\\u000a produced in the expansion region of the beam, and are subsequently ionized by “fly through” electron impact (EI) ionization,\\u000a which results in a mass spectrum

  1. Determination of double bond position in conjugated dienes by chemical ionization mass spectrometry with isobutane

    Microsoft Academic Search

    Robert E. Doolittle; J. H. Tumlinson; A. Proveaux

    1985-01-01

    The chemical ionization (CI) mass spectra of a series of functionalized conjugated dienes, including aldehydes, alcohols, formates, acetates, and hydrocarbons were investigated to determine whether fragmentations occur that are characteristic of the position of the conjugated system within the hydrocarbon chain. CI with isobutane as ionizing gas produces structure-specific fragment ions with m\\/z ratios that can be used to locate

  2. 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 ...

  3. Double ionization of a negative hydrogen ion by positron and electron impact at high and intermediate energies

    Microsoft Academic Search

    D. Ghosh; B. Nath; C. Sinha

    2003-01-01

    Double ionization (DI) of a negative hydrogen ion (H-) has been studied in a comparative manner by e and e+ impacts at high and intermediate incident energies using the framework of the Coulomb-Born approximation. Unlike other existing theories for the DI process of H-, the present model is the first one to take account of the residual Coulomb potential between

  4. 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...

  5. Insight into acid-base nucleation experiments by comparison of the chemical composition of positive, negative, and neutral clusters.

    PubMed

    Bianchi, Federico; Praplan, Arnaud P; Sarnela, Nina; Dommen, Josef; Kürten, Andreas; Ortega, Ismael K; Schobesberger, Siegfried; Junninen, Heikki; Simon, Mario; Tröstl, Jasmin; Jokinen, Tuija; Sipilä, Mikko; Adamov, Alexey; Amorim, Antonio; Almeida, Joao; Breitenlechner, Martin; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Kangasluoma, Juha; Keskinen, Helmi; Kim, Jaeseok; Kirkby, Jasper; Laaksonen, Ari; Lawler, Michael J; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Mathot, Serge; Onnela, Antti; Petäjä, Tuukka; Riccobono, Francesco; Rissanen, Matti P; Rondo, Linda; Tomé, António; Virtanen, Annele; Viisanen, Yrjö; Williamson, Christina; Wimmer, Daniela; Winkler, Paul M; Ye, Penglin; Curtius, Joachim; Kulmala, Markku; Worsnop, Douglas R; Donahue, Neil M; Baltensperger, Urs

    2014-12-01

    We investigated the nucleation of sulfuric acid together with two bases (ammonia and dimethylamine), at the CLOUD chamber at CERN. The chemical composition of positive, negative, and neutral clusters was studied using three Atmospheric Pressure interface-Time Of Flight (APi-TOF) mass spectrometers: two were operated in positive and negative mode to detect the chamber ions, while the third was equipped with a nitrate ion chemical ionization source allowing detection of neutral clusters. Taking into account the possible fragmentation that can happen during the charging of the ions or within the first stage of the mass spectrometer, the cluster formation proceeded via essentially one-to-one acid-base addition for all of the clusters, independent of the type of the base. For the positive clusters, the charge is carried by one excess protonated base, while for the negative clusters it is carried by a deprotonated acid; the same is true for the neutral clusters after these have been ionized. During the experiments involving sulfuric acid and dimethylamine, it was possible to study the appearance time for all the clusters (positive, negative, and neutral). It appeared that, after the formation of the clusters containing three molecules of sulfuric acid, the clusters grow at a similar speed, independent of their charge. The growth rate is then probably limited by the arrival rate of sulfuric acid or cluster-cluster collision. PMID:25406110

  6. Negative electrospray ionization low-energy tandem mass spectrometry of hydroxylated fatty acids: a mechanistic study.

    PubMed

    Moe, Morten K; Strøm, Morten B; Jensen, Einar; Claeys, Magda

    2004-01-01

    Recently, we reported that by converting olefinic fatty acids to their saturated vicinally 1,2-di-hydroxylated derivatives, abundant ions indicative for hydroxyl group locations are produced by negative electrospray ionization low-energy tandem mass spectrometry, allowing the assignment of the olefinic site in the native fatty acid. In this report the mechanisms whereby the characteristic ions are produced are investigated. The mono-hydroxylated fatty acid, 12-hydroxyoctadecanoic acid, served as a model for the more complex 12,13-dihydroxyoctadecanoic acid, and fragmentation mechanisms accounting for the most abundant product ions generated from their deprotonated molecules are proposed. In general, three different mechanisms are proposed to operate in the formation of the observed product ions: (i) step-wise charge-remote homolytic cleavages, (ii) step-wise charge-proximate homolytic cleavages, and (iii) concerted charge-directed rearrangement reactions involving bond formation(s) and heterolytic cleavages. Support for the proposed mechanisms was achieved by investigating the deuterium- and oxygen-18-labeled isotopomers of both compounds. PMID:15282772

  7. Chemical ionization of pentacarbonylrhenium halides in vapor of water, methanol, or ethanol

    SciTech Connect

    Bogdanov, V.A.; Savel'ev, Y.I.; Shchelokov, R.N.

    1986-05-01

    This paper studies the behavior of pentacarbonylrhenium (PCR) halides in chemical ionization in water, methanol, ethanol, or acetone in the vapor phase. The mass spectra is shown for the chemical ionization of the mixture of PCR chloride and PCR bromide, normalized on the maximum-intensity peak. The study shows that the most active group in the complexes Re(CO)/sub 5/X, susceptible to detachment or replacement in ionized vapor of water or certain simple alcohols, is a halogen atom that is omega-bonded to the metal atom. Data on the chemical ionization of halogen-substituted organic compounds also indicate that the halogen atoms in these compounds are quite readily split off, usually in the form of the hydrogen halide.

  8. Analysis of bitter limonoids in citrus juices by atmospheric pressure chemical ionization and electrospray ionization liquid chromatography-mass spectrometry.

    PubMed

    Manners, Gary D; Breksa, Andrew P; Schoch, Thomas K; Hidalgo, Marlene B

    2003-06-18

    Improved analytical techniques for bitter limonoids in citrus and citrus juices can expedite the evaluation of freeze-induced citrus damage for citrus growers and juice quality for citrus juice producers. Microbore normal-phase and reverse-phase chromatography coupled to a mass spectrometer operating in a positive ion atmospheric pressure chemical ionization and electrospray ionization modes were found to be rapid, selective, and sensitive methods for the analysis of the bitter limonoids limonin and nomilin in citrus juices. Analysis was performed on a chloroform extract of citrus juice to which an internal standard was added. The methods are capable of detecting citrus limonoids in citrus juice in the 60-200 picogram range and quantifying citrus juice limonoids in concentrations as low as 120 picograms. An accurate "total limonoid bitterness" in citrus juice, as represented by the combined occurrence of limonin and nomilin, is easily determined by these methods. PMID:12797731

  9. Laser Isotope Separation in Atomic Vapour:. PhotoChemical Method VS. PhotoIonization One

    Microsoft Academic Search

    P. A. Bokhan; N. V. Fateyev; D. E. Zakrevskiy; V. V. Buchanov; M. A. Kazaryan

    2010-01-01

    Two methods of laser isotope separation in atomic vapour are compared. The first of them is a well developed Photo-ionization method. The other method is based on isotope-selective excitation of long-living atomic states and subsequent chemical reaction of excited atom with special reagents. It is shown that this method has some principal advantages compared to Photo-ionization method.

  10. Method for the separate determination of electron density and negative-ion density in a dense ionized gas

    Microsoft Academic Search

    M. A. Kanatenko

    1981-01-01

    A method for the separate determination of electron density and negative-ion density in a dense gas ionized by alpha particles from a radioisotope is experimentally demonstrated. The method is based on the use of a high-frequency electronic filter which crosses at the anode the nonself-sustained Thomson discharge column. The HF filter consists of thin parallel wires between which an ac-field

  11. Low blank rhenium isotope ratio determinations by V2O5 coated nickel filaments using negative thermal ionization mass spectrometry

    Microsoft Academic Search

    Thomas Walczyk; Erhard H. Hebeda; Klaus G. Heumann

    1994-01-01

    Thenium isotope ratio determinations are, in principle, possible by negative thermal ionization mass spectrometry (NTI-MS). Relatively high rhenium blanks from the commonly-used filament materials prevent accurate isotope ratio determinations, especially for small rhenium sample amounts which are of importance, for example, in geochronology in connection with the Re\\/Os dating method. Platinum and nickel filaments were tested by different preparation techniques

  12. 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.

  13. Negative Differential Resistance of CaF 2/CdF 2 Triple-Barrier Resonant-Tunneling Diode on Si(111) Grown by Partially Ionized Beam Epitaxy

    NASA Astrophysics Data System (ADS)

    Watanabe, Masahiro; Aoki, Yuichi; Saito, Wataru; Tsuganezawa, Mika

    1999-02-01

    Room-temperature negative differential resistance (NDR) of triple-barrier cadmium di-fluoride (CdF2)/calcium di-fluoride (CaF2) heterostructure resonant-tunneling diode (RTD) on a Si(111) substrate has been demonstrated. CdF2/CaF2 multilayered heterostructures were grown on a Si(111) substrate using partially ionized beam epitaxy to obtain atomically flat interfaces. The RTD structures, which consist of triple CaF2 energy barriers and double CdF2 quantum wells, were fabricated by electron beam (EB) lithography and dry etching to avoid thermal and chemical damage to the CdF2 layers. In the current-voltage characteristics of the RTD, NDR was clearly observed even at room temperature and the maximum peak-to-valley (P/V) ratio was about 6.

  14. Calcification of synthetic polymers functionalized with negatively ionizable groups: A critical review

    Microsoft Academic Search

    Traian V. Chirila; Zainuddin

    2007-01-01

    The functionalization of polymers with ionizable carboxyl and oxyphosphorus (phosphate, phosphonate, etc.) groups has been frequently advocated as a method of enhancing their calcification capacity as a prerequisite in certain biomedical applications. However, the existing literature regarding in vitro and in vivo experimental calcification of functionalized polymers is rather a collection of contradictory reports. Some investigators found that carboxyl or

  15. NON-NEGATIVE MATRIX FACTORIZATION WITH ORTHOGONALITY CONSTRAINTS FOR CHEMICAL AGENT DETECTION IN RAMAN SPECTRA

    E-print Network

    Adali, Tulay

    - tical F-test and the relative strength of each chemical identi- fied as present in the measurementNON-NEGATIVE MATRIX FACTORIZATION WITH ORTHOGONALITY CONSTRAINTS FOR CHEMICAL AGENT DETECTION in the chemical agent detection problem. 1. INTRODUCTION Raman spectroscopy can be used for detecting a wide range

  16. 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

  17. Influence of ionization on the Gupta and on the Park chemical models

    NASA Astrophysics Data System (ADS)

    Morsa, Luigi; Zuppardi, Gennaro

    2014-12-01

    This study is an extension of former works by the present authors, in which the influence of the chemical models by Gupta and by Park was evaluated on thermo-fluid-dynamic parameters in the flow field, including transport coefficients, related characteristic numbers and heat flux on two current capsules (EXPERT and Orion) during the high altitude re-entry path. The results verified that the models, even computing different air compositions in the flow field, compute only slight different compositions on the capsule surface, therefore the difference in the heat flux is not very relevant. In the above mentioned studies, ionization was neglected because the velocities of the capsules (about 5000 m/s for EXPERT and about 7600 m/s for Orion) were not high enough to activate meaningful ionization. The aim of the present work is to evaluate the incidence of ionization, linked to the chemical models by Gupta and by Park, on both heat flux and thermo fluid-dynamic parameters. The present computer tests were carried out by a direct simulation Monte Carlo code (DS2V) in the velocity interval 7600-12000 m/s, considering only the Orion capsule at an altitude of 85 km. The results verified what already found namely when ionization is not considered, the chemical models compute only a slight different gas composition in the core of the shock wave and practically the same composition on the surface therefore the same heat flux. On the opposite, the results verified that when ionization is considered, the chemical models compute different compositions in the whole shock layer and on the surface therefore different heat flux. The analysis of the results relies on a qualitative and a quantitative evaluation of the effects of ionization on both chemical models. The main result of the study is that when ionization is taken into account, the Park model is more reactive than the Gupta model; consequently, the heat flux computed by Park is lower than the one computed by Gupta; using the Gupta model, in the design of a thermal protection system, is recommended.

  18. Evaluating the Utility of an Atmospheric Pressure Chemical Ionization Mass Spectrometer for Analyzing Organic Peroxides

    NASA Astrophysics Data System (ADS)

    Jameer, A.; Hastie, D. R.

    2013-12-01

    Secondary organic aerosols (SOA) are known to affect the earth's radiation budget through its ability to scatter and absorb radiation. Consequently, the mechanisms and factors that influence SOA composition and formation are poorly understood. However, recent modeling studies coupled with smog chamber experiments suggest that organic peroxides (organic hydroperoxides and peroxyhemiacetals) might be a major component of SOA composition under low NOx conditions. This study utilized an atmospheric pressure chemical ionization mass spectrometer (APCI-MS) in the positive mode to detect organic peroxides. Mass spectra of organic peroxides analyzed in this study show excessive fragmentation during ionization with protonated water clusters. It was believed that intact ions were not found due to decomposition in the ion source. Future work will explore new reagents for ionization to reduce fragmentation during analysis.

  19. Comparison of electrospray ionization and atmospheric chemical ionization coupled with the liquid chromatography-tandem mass spectrometry for the analysis of cholesteryl esters.

    PubMed

    Lee, Hae-Rim; Kochhar, Sunil; Shim, Soon-Mi

    2015-01-01

    The approach of two different ionization techniques including electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was tested for the analysis of cholesteryl esters (CEs). The retention time (RT), signal intensity, protonated ion, and product ion of CEs were compared between ESI and APCI. RT of CEs from both ionizations decreased with increasing double bonds, while it increased with longer carbon chain length. The ESI process generated strong signal intensity of precursor ions corresponding to [M+Na](+) and [M+NH4](+) regardless of the number of carbon chains and double bonds in CEs. On the other hand, the APCI process produced a protonated ion of CEs [M+H](+) with a weak signal intensity, and it is selectively sensitive to detect precursor ions of CEs with unsaturated fatty acids. The ESI technique proved to be effective in ionizing more kinds of CEs than the APCI technique. PMID:25873970

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

    PubMed Central

    Lee, Hae-Rim; Kochhar, Sunil; Shim, Soon-Mi

    2015-01-01

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

  1. 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

  2. Cluster chemical ionization and deuterium exchange mass spectrometry in supersonic molecular Beams.

    PubMed

    Dagan, S; Amirav, A

    1996-06-01

    A cluster-based chemical ionization method has been developed that produces protonated molecular ions from molecules introduced through a supersonic molecular beam interface. Mixed clusters of the analyte and a clustering agent (water or methanol) are produced in the expansion region of the beam, and are subsequently ionized by "fly through" electron impact (EI) ionization, which results in a mass spectrum that is a combination of protonated molecular ion peaks together with the conventional EI fragmentation pattern. The technique is presented and discussed as a tool complementary to electron impact ionization in supersonic molecular beams. Surface-induced dissociation on a rhenium oxide surface is also applied to simplify the mass spectra of clusters and reveal the analyte spectrum. The high gas flow rates involved with the supersonic molecular beam interface that enable the easy introduction of the clustering agents also have been used to introduce deuterating agents. An easy-to-use, fast, and routine on-line deuterium exchange method was developed to exchange active hydrogens (NH, OH). This method, combined with electron impact ionization, is demonstrated and discussed in terms of the unique information available through the EI fragmentation patterns, its ability to help in isomer identification, and possible applications with fast gas chromatography-mass spectrometry in supersonic molecular beams. PMID:24203427

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

    PubMed

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

    2002-09-01

    The ionization pathways were determined for sets of isomeric non-polar hydrocarbons (structural isomers, cis/trans isomers) using ion mobility spectrometry and mass spectrometry with different techniques of atmospheric pressure chemical ionization to assess the influence of structural features on ion formation. Depending on the structural features, different ions were observed using mass spectrometry. Unsaturated hydrocarbons formed mostly [M - 1]+ and [(M - 1)2H]+ ions while mainly [M - 3]+ and [(M - 3)H2O]+ ions were found for saturated cis/trans isomers using photoionization and 63Ni ionization. These ionization methods and corona discharge ionization were used for ion mobility measurements of these compounds. Different ions were detected for compounds with different structural features. 63Ni ionization and photoionization provide comparable ions for every set of isomers. The product ions formed can be clearly attributed to the structures identified. However, differences in relative abundance of product ions were found. Although corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra detected are complex and differ from those obtained with 63Ni ionization and photoionization. PMID:12322955

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

    NASA Technical Reports Server (NTRS)

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

    2002-01-01

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

  5. Chemical ionization tandem mass spectrometer for the in situ measurement of methyl hydrogen peroxide

    SciTech Connect

    St Clair, Jason M.; McCabe, David C. [Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91125 (United States); Crounse, John D. [Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125 (United States); Steiner, Urs [Varian, Inc., Santa Clara, California 95051 (United States); Wennberg, Paul O. [Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91125 (United States); Division of Engineering and Applied Science, California Institute of Technology, Pasadena, California 91125 (United States)

    2010-09-15

    A new approach for measuring gas-phase methyl hydrogen peroxide [(MHP) CH{sub 3}OOH] utilizing chemical ionization mass spectrometry is presented. Tandem mass spectrometry is used to avoid mass interferences that hindered previous attempts to measure atmospheric CH{sub 3}OOH with CF{sub 3}O{sup -} clustering chemistry. CH{sub 3}OOH has been successfully measured in situ using this technique during both airborne and ground-based campaigns. The accuracy and precision for the MHP measurement are a function of water vapor mixing ratio. Typical precision at 500 pptv MHP and 100 ppmv H{sub 2}O is {+-}80 pptv (2 sigma) for a 1 s integration period. The accuracy at 100 ppmv H{sub 2}O is estimated to be better than {+-}40%. Chemical ionization tandem mass spectrometry shows considerable promise for the determination of in situ atmospheric trace gas mixing ratios where isobaric compounds or mass interferences impede accurate measurements.

  6. Bimolecular and unimolecular contributions to the disparate self-chemical ionizations of ? Pinene and camphene isomers

    Microsoft Academic Search

    Touradj Solouki; Jan E. Szulejko

    2007-01-01

    The contributions of molecular and fragment ions toward the disparate self-chemical ionization (SCI) of ?-pinene and camphene isomers were investigated. A kinetic model was constructed to predict the SCI outcomes for these two\\u000a C10H16 isomers. A major portion of the camphene molecular ions (isolated 500 ms after the 10 ms EI event at 24 eV) unimolecularly\\u000a dissociated within 200 s

  7. 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.

  8. 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.

  9. 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.

  10. Chemical Ionization Mass Spectrometer (CIMS) Shanhu Lee, Kent State University (http://www.personal.kent.edu/~slee19/)

    E-print Network

    Lee, Shan-Hu

    . Kosciuch, Proton transfer mass spectrometry at high drift tube pressure, Int. J. Mass. Spec. 223-224, 507Chemical Ionization Mass Spectrometer (CIMS) Shanhu Lee, Kent State University (http ionization mass spectrometry (PTR-CIMS). A typical CIMS instrument can be constructed from an ion source

  11. 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...

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

    Laser-induced acoustic desorption (LIAD) was successfully coupled to a conventional atmospheric pressure chemical ionization (APCI) source in a commercial 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. From the four APCI reagent systems tested, neat carbon disulfide provided the best results. 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 but minor amount of fragmentation was observed for these two 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 predominantly form stable molecular ions.

  13. Atmospheric pressure laser-induced acoustic desorption chemical ionization mass spectrometry for analysis of saturated hydrocarbons.

    PubMed

    Nyadong, Leonard; Quinn, John P; Hsu, Chang S; Hendrickson, Christopher L; Rodgers, Ryan P; Marshall, Alan G

    2012-08-21

    We present atmospheric pressure laser-induced acoustic desorption chemical ionization (AP/LIAD-CI) with O(2) carrier/reagent gas as a powerful new approach for the analysis of saturated hydrocarbon mixtures. Nonthermal sample vaporization with subsequent chemical ionization generates abundant ion signals for straight-chain, branched, and cycloalkanes with minimal or no fragmentation. [M - H](+) is the dominant species for straight-chain and branched alkanes. For cycloalkanes, M(+•) species dominate the mass spectrum at lower capillary temperature (<100 °C) and [M - H](+) at higher temperature (>200 °C). The mass spectrum for a straight-chain alkane mixture (C(21)-C(40)) shows comparable ionization efficiency for all components. AP/LIAD-CI produces molecular weight distributions similar to those for gel permeation chromatography for polyethylene polymers, Polywax 500 and Polywax 655. Coupling of the technique to Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) for the analysis of complex hydrocarbon mixtures provides unparalleled mass resolution and accuracy to facilitate unambiguous elemental composition assignments, e.g., 1754 peaks (rms error = 175 ppb) corresponding to a paraffin series (C(12)-C(49), double-bond equivalents, DBE = 0) and higher DBE series corresponding to cycloparaffins containing one to eight rings. Isoabundance-contoured plots of DBE versus carbon number highlight steranes (DBE = 4) of carbon number C(27)-C(30) and hopanes of C(29)-C(35) (DBE = 5), with sterane-to-hopane ratio in good agreement with field ionization (FI) mass spectrometry analysis, but performed at atmospheric pressure. The overall speciation of nonpolar, aliphatic hydrocarbon base oil species offers a promising diagnostic probe to characterize crude oil and its products. PMID:22881221

  14. Low blank isotope ratio measurements of rhenium, osmium, and platinum using tantalum filaments with negative thermal ionization mass spectrometry.

    PubMed

    Hattori, K; Menagh, D P; Cole, T J

    1998-10-01

    Platinum is most commonly used as a filament for Re and Os isotopic measurements, but it contains impurities of Re and Os. Tantalum is low in platinum group elements (PGE) and in Re, but it is not used for negative thermal ionization mass spectrometry because of high electron emission and high reactivity with O(2). High thermal electron emission from Ta distorts the preoptimized ion source optics. In addition, Ta consumes O(2), leaving little for samples, but O(2) is essential for isotopic ratio measurements of PGE and Re as they are measured as negatively charged oxides, such as OsO(3)(-) and PtO(2)(-). These problems are solved by prebaking a filament to remove tantalum oxides before sample loading, keeping relatively high filament temperatures and high O(2) pressures (P(O)((2))) during the sample run, and lowering the potential difference between the filament and the draw-out plate. At P(O)((2)) of ?1 × 10(-)(5) Torr in the source, strong (>10 V) stable (>6 h) peaks of ReO(4)(-), OsO(3)(-), and PtO(2)(-) are obtained at 750 °C for Re, 850 °C for Pt, and over 900 °C for Os. Accurate isotopic ratio measurements of Re, Os, and Pt at picogram levels are possible using Ta filaments. PMID:21651247

  15. 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.

  16. Real-time monitoring of volatile organic compounds using chemical ionization mass spectroscopy: Final report

    SciTech Connect

    Thornberg, S.M.; Mowry, C.D.; Keenan, M.R.; Bender, S.F.A. [Sandia National Labs., Albuquerque, NM (United States). Gas Analysis Lab.; Owen, T. [Intel Corp., Rio Rancho, NM (United States)

    1997-04-01

    Volatile organic compound (VOC) emission to the atmosphere is of great concern to semiconductor manufacturing industries, research laboratories, the public, and regulatory agencies. Some industries are seeking ways to reduce emissions by reducing VOCs at the point of use (or generation). This paper discusses the requirements, design, calibration, and use of a sampling inlet/quadrupole mass spectrometer system for monitoring VOCs in a semiconductor manufacturing production line. The system uses chemical ionization to monitor compounds typically found in the lithography processes used to manufacture semiconductor devices (e.g., acetone, photoresist). The system was designed to be transportable from tool to tool in the production line and to give the operator real-time feedback so the process(es) can be adjusted to minimize VOC emissions. Detection limits ranging from the high ppb range for acetone to the low ppm range fore other lithography chemicals were achieved using chemical ionization mass spectroscopy at a data acquisition rate of approximately 1 mass spectral scan (30 to 200 daltons) per second. A demonstration of exhaust VOC monitoring was performed at a working semiconductor fabrication facility during actual wafer processing.

  17. 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.

  18. 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

  19. Fine Structure and Ionization Energy of the 1 s 2 s 2 p 4P State of the Helium Negative Ion He-

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    The fine structure and ionization energy of the 1 s 2 s 2 p 4P state of the helium negative ion He- are calculated in Hylleraas coordinates, including relativistic and QED corrections up to O (?4m c2) , O ((? /M )?4m c2) , O (?5m c2) , and O ((? /M )?5m c2) . Higher order corrections are estimated for the ionization energy. A comparison is made with other calculations and experiments. We find that the present results for the fine structure splittings agree with experiment very well. However, the calculated ionization energy deviates from the experimental result by about 1 standard deviation. The estimated theoretical uncertainty in the ionization energy is much less than the experimental accuracy.

  20. 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.

  1. Detection of aqueous phase chemical warfare agent degradation products by negative mode ion mobility time-of-flight mass spectrometry [IM(tof)MS].

    PubMed

    Steiner, Wes E; Harden, Charles S; Hong, Feng; Klopsch, Steve J; Hill, Herbert H; McHugh, Vincent M

    2006-02-01

    The use of negative ion monitoring mode with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer [IM(tof)MS] to detect chemical warfare agent (CWA) degradation products from aqueous phase samples has been determined. Aqueous phase sampling used a traditional electrospray ionization (ESI) source for sample introduction and ionization. Certified reference materials (CRM) of CWA degradation products for the detection of Schedule 1, 2, or 3 toxic chemicals or their precursors as defined by the chemical warfare convention (CWC) treaty verification were used in this study. A mixture of six G-series nerve related CWA degradation products (EMPA, IMPA, EHEP, IHEP, CHMPA, and PMPA) and their related collision induced dissociation (CID) fragment ions (MPA and EPA) were found in each case to be clearly resolved and detected using the IM(tof)MS instrument in negative ion monitoring mode. Corresponding ions, masses, drift times, K(o) values, and signal intensities for each of the CWA degradation products are reported. PMID:16413205

  2. Atmospheric pressure chemical ionization mass spectrometry of pyridine and isoprene: potential breath exposure and disease biomarkers.

    PubMed

    Kapishon, Vitaliy; Koyanagi, Gregory K; Blagojevic, Voislav; Bohme, Diethard K

    2013-06-01

    Volatile organic compounds (VOCs) in exhaled human breath can serve as potential disease-specific and exposure biomarkers and therefore can reveal information about a subject's health and environment. Pyridine, a VOC marker for exposure to tobacco smoke, and isoprene, a liver disease biomarker, were studied using atmospheric pressure chemical ionization mass spectrometry (APCI-MS). While both molecules could be detected in low-ppb levels, interactions of the ionized analytes with their neutral forms and ambient air led to unusual ion/molecule chemistry. The result was a highly dynamic system and a nonlinear response to changes in analyte concentration. Increased presence of ambient water was found to greatly enhance the detection limit of pyridine and only slightly decrease that of isoprene. APCI-MS is shown to be a promising analytical tool in breath analysis with good detection limits, but its application requires a better understanding of the ion/molecule chemistry that may affect VOC quantification from a chemically complex system such as human breath. PMID:23579200

  3. 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.

  4. Negative surface ionization mass spectrometry for real-time monitoring of iodine molecules in process off-gas

    SciTech Connect

    Kishi, Hiroshi (Oyama National College of Technology (Japan)); Fujii, Toshihiro (National Inst. for Environmental Studies, Tsukuba (Japan))

    1994-12-15

    Negative surface ionization mass spectrometry is being developed for continuous measurement of iodine found in the atmospheric environment as a result of nuclear fuel reprocessing. Studies have been made on a series of low work function surface materials (CaCO[sub 3]-SrCO[sub 3]-CaCO[sub 3], BaCO[sub 3]-SrCO[sub 3], LaB[sub 6]) with the intent of developing improved methods for iodine analysis, particularly at the environmental level (ppb concentration range). The results demonstrate the feasibility of performing real-time measurements of the trace amount of iodine encountered in process off-gas by use of a CaCO[sub 3]-SrCO[sub 3]-CaCO[sub 3]-coated rhenium filament emitter. This emitter surface with thermoelectronic work function [phi] at 2.0 eV gives 37.5 times greater sensitivity than the established LaB[sub 6] emitter for iodine analysis. 22 refs., 6 figs., 1 tab.

  5. Selective reaction monitoring of negative electrospray ionization acetate adduct ions for the bioanalysis of dapagliflozin in clinical studies.

    PubMed

    Ji, Qin C; Xu, Xiaohui; Ma, Eric; Liu, Jane; Basdeo, Shenita; Liu, Guowen; Mylott, William; Boulton, David W; Shen, Jim X; Stouffer, Bruce; Aubry, Anne-Françoise; Arnold, Mark E

    2015-03-17

    Dapagliflozin (Farxiga), alone, or in the fixed dose combination with metformin (Xigduo), is an orally active, highly selective, reversible inhibitor of sodium-glucose cotransporter type 2 (SGLT2) that is marketed in United States, Europe, and many other countries for the treatment of type 2 diabetes mellitus. Here we report a liquid chromatography-tandem mass spectrometry (LC-MS/MS) bioanalytical assay of dapagliflozin in human plasma. A lower limit of quantitation (LLOQ) at 0.2 ng/mL with 50 ?L of plasma was obtained, which reflects a 5-fold improvement of the overall assay sensitivity in comparison to the previous most sensitive assay using the same mass spectrometry instrumentation. In this new assay, acetate adduct ions in negative electrospray ionization mode were used as the precursor ions for selective reaction monitoring (SRM) detection. Sample preparation procedures and LC conditions were further developed to enhance the column life span and achieve the separation of dapagliflozin from potential interferences, especially its epimers. The assay also quantifies dapagliflozin's major systemic circulating glucuronide metabolite, BMS-801576, concentrations in human plasma. The assay was successfully transferred to contract research organizations (CROs), validated, and implemented for the sample analysis of pediatric and other critical clinical studies. This assay can be widely used for bioanalytical support of future clinical studies for the newly approved drug Farxiga or any combination therapy containing dapagliflozin. PMID:25671589

  6. Quasi-trapping chemical ionization source based on a commercial VUV lamp for time-of-flight mass spectrometry.

    PubMed

    Chen, Ping; Hou, Keyong; Hua, Lei; Xie, Yuanyuan; Zhao, Wuduo; Chen, Wendong; Chen, Chuang; Li, Haiyang

    2014-02-01

    The application of VUV lamp-based single photon ionization (SPI) was limited due to low photon energy and poor photon flux density. In this work, we designed a quasi-trapping chemical ionization (QT-CI) source with a commercial VUV 10.6 eV krypton lamp for time-of-flight mass spectrometry. The three electrode configuration ion source with RF voltage on the second electrode constitutes a quasi-trapping region, which has two features: accelerating the photoelectrons originated from the photoelectric effect with VUV light to trigger the chemical ionization through ion-molecule reaction and increasing the collisions between reactant ion O2(+) and analyte molecules to enhance the efficiency of chemical ionization. Compared to single SPI based on VUV krypton lamp, the QT-CI ion source not only apparently improved the sensitivity (e.g., 12-118 fold enhancement were achieved for 13 molecules, including aromatic hydrocarbon, chlorinated hydrocarbon, hydrogen sulfide, etc.) but also extended the range of ionizable molecules with ionization potential (IP) higher than 10.6 eV, such as propane, dichloroethane, and trichloromethane. PMID:24428693

  7. 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.

  8. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol - a laboratory and field study

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Brüggemann, M.; Ehn, M.; Junninen, H.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2012-08-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was increased by a factor of 7.5 to 11 (e.g. ~40 ng m-3 for pinonic acid) by using the miniature Versatile Aerosol Concentration Enrichment System (mVACES) upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards - pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total sub-micron organic aerosol mass was estimated to be about 60%. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94) demonstrates soft ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (?-pinene and ?3-carene) cannot account for all of the measured fragments, which illustrates the complexity of ambient aerosol and possibly indicates unidentified or underestimated biogenic SOA precursor in the boreal forest.

  9. Kinetic and Thermodynamic Control of Protonation in Atmospheric Pressure Chemical Ionization

    NASA Astrophysics Data System (ADS)

    Chai, Yunfeng; Hu, Nan; Pan, Yuanjiang

    2013-07-01

    For p-(dimethylamino)chalcone ( p-DMAC), the N atom is the most basic site in the liquid phase, whereas the O atom possesses the highest proton affinity in the gas phase. A novel and interesting observation is reported that the N- and O-protonated p-DMAC can be competitively produced in atmospheric pressure chemical ionization (APCI) with the change of solvents and ionization conditions. In neat methanol or acetonitrile, the protonation is always under thermodynamic control to form the O-protonated ion. When methanol/water or acetonitrile/water was used as the solvent, the protonation is kinetically controlled to form the N-protonated ion under conditions of relatively high infusion rate and high concentration of water in the mixed solvent. The regioselectivity of protonation of p-DMAC in APCI is probably attributed to the bulky solvent cluster reagent ions (SnH+) and the analyte having different preferred protonation sites in the liquid phase and gas phase.

  10. 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.

  11. Characterization of aromatized biomarkers by GC/MS/MS with chemical ionization

    SciTech Connect

    Hsu, C.S.; Dechert, G.J. [Exxon Research and Engineering Co., Annandale, NJ (United States); Schaps, M.E.; Hieshima, G.B. [Exxon Production Research Co., Houston, TX (United States)

    1995-12-31

    Although present in trace amounts, biomarkers are extensively studied by geochemists to understand paleotransformation processes that convert ancient living organisms into petroleum components and to assess age, maturity and source input of the petroleum. Most studied are saturated biomarkers that yield both molecular and characteristic fragment ions under high voltage (50-70 V) electron-impact ionization (HV/EI) conditions. Linking these molecular and fragment ions derived from saturated hydrocarbon compounds using GC/MS/MS resolves coeluting components and provides less ambiguous geochemical information than GC/MS. The same GC/MS/MS techniques cannot be applied to aromatized biomarkers because they yield trace or no molecular ions under HV/EI conditions. To overcome these difficulties, chemical ionization (CI) has been studied for producing ionic species more representative of molecules. Among the reagent gases evaluated, isobutane yields predominantly protonated molecular ions while methane and ammonia yield more than one type of pseudomolecular ions. Thus, isobutane is the gas of choice for the aromatic biomarkers using GC/MS/MS with CI. This analytical technique is particularly useful for resolving overlapping monoaromatic steranes (MAS). Characterization of aromatic biomarkers more accurately would help to explain better the maturation mechanism of petroleum molecules under thermal stress.

  12. Ion/molecule reactions to chemically deconvolute the electrospray ionization mass spectra of synthetic polymers.

    PubMed

    Lennon, John D; Cole, Scott P; Glish, Gary L

    2006-12-15

    A new approach has been developed to analyze synthetic polymers via electrospray ionization mass spectrometry. Ion/molecule reactions, a unique feature of trapping instruments such as quadrupole ion trap mass spectrometers, can be used to chemically deconvolute the molecular mass distribution of polymers from the charge-state distribution generated by electrospray ionization. The reaction involves stripping charge from multiply charged oligomers to reduce the number of charge states. This reduces or eliminates the overlapping of oligomers from adjacent charge states. 15-Crown-5 was used to strip alkali cations (Na+) from several narrow polydisperse poly(ethylene glycol) standards. The charge-state distribution of each oligomer is reduced to primarily one charge state. Individual oligomers can be resolved, and the average molecular mass and polydispersities can be calculated for the polymers examined here. In most cases, the measured number-average molecular mass values are within 10% of the manufacturers' reported values obtained by gel permeation chromatography. The polydispersity was typically underestimated compared to values reported by the suppliers. Mn values were obtained with 0.5% RSD and are independent, over several orders of magnitude, of the polymer and cation concentration. The distributions that were obtained fit quite well to the Gaussian distribution indicating no high- or low-mass discriminations. PMID:17165841

  13. Negative-Energy Spinors and the Fock Space of Lattice Fermions at Finite Chemical Potential

    E-print Network

    E. Mendel; L. Polley

    1994-06-10

    Recently it was suggested that the problem of species doubling with Kogut-Susskind lattice fermions entails, at finite chemical potential, a confusion of particles with antiparticles. What happens instead is that the familiar correspondence of positive-energy spinors to particles, and of negative-energy spinors to antiparticles, ceases to hold for the Kogut-Susskind time derivative. To show this we highlight the role of the spinorial ``energy'' in the Osterwalder-Schrader reconstruction of the Fock space of non-interacting lattice fermions at zero temperature and nonzero chemical potential. We consider Kogut-Susskind fermions and, for comparison, fermions with an asymmetric one-step time derivative.

  14. A chemical ionization selected ion monitoring assay for methylphenidate and ritalinic acid.

    PubMed

    Iden, C R; Hungund, B L

    1979-10-01

    A methane chemical ionization quantitative assay for methylphenidate and its major metabolite, ritalinic acid, is described. Methylphenidate and the internal standard, ethylphenidate, were extracted from plasma samples and derivatized to prevent thermal decomposition in the gas chromatography. Ritalinic acid was esterified with diazomethane and extracted as methylphenidate. The intensity of the protonated molecular ion of the derivatized drug and internal standard was measured by selected ion monitoring. Calibration curves were prepared from drug standards dissolved in drug-free plasma, and the lower limit of the curves extended to 0.5 ng methylphenidate per ml plasma. The method was used to generate plasma decay curves for pediatric patients undergoing methylphenidate therapy. PMID:526558

  15. 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.

  16. Atmospheric amines and ammonia measured with a chemical ionization mass spectrometer (CIMS)

    NASA Astrophysics Data System (ADS)

    You, Y.; Kanawade, V. P.; de Gouw, J. A.; Guenther, A. B.; Madronich, S.; Sierra-Hernández, M. R.; Lawler, M.; Smith, J. N.; Takahama, S.; Ruggeri, G.; Koss, A.; Olson, K.; Baumann, K.; Weber, R. J.; Nenes, A.; Guo, H.; Edgerton, E. S.; Porcelli, L.; Brune, W. H.; Goldstein, A. H.; Lee, S.-H.

    2014-11-01

    We report measurements of ambient amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a southeastern US forest and a moderately polluted midwestern site during the summer. At the forest site, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected, and they both showed temperature dependencies. Aerosol-phase amines measured thermal-desorption chemical ionization mass spectrometer (TDCIMS) showed a higher mass fraction in the evening with cooler temperatures and lower in the afternoon with warmer temperatures, a trend opposite to the gas-phase amines. Concentrations of aerosol-phase primary amines measured with Fourier transform infrared spectroscopy (FTIR) from micron and submicron particles were 2 orders of magnitude higher than the gas-phase amines. These results indicate that gas to particle conversion is one of the major processes that control the ambient amine concentrations at this forest site. Temperature dependencies of C3-amines and ammonia also imply reversible processes of evaporation of these nitrogen-containing compounds from soil surfaces in daytime and deposition to soil surfaces at nighttime. During the transported biomass burning plume events, various amines (C1-C6) appeared at the pptv level, indicating that biomass burning is a substantial source of amines in the southeastern US. At the moderately polluted Kent site, there were higher concentrations of C1- to C6-amines (pptv to tens of pptv) and ammonia (up to 6 ppbv). C1- to C3-amines and ammonia were well correlated with the ambient temperature. C4- to C6-amines showed frequent spikes during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Higher amine concentrations measured at the polluted site than at the rural forested site highlight the importance of constraining anthropogenic emission sources of amines.

  17. [Development of a chemical ionization time-of-flight mass spectrometer for continuous measurements of atmospheric hydroxyl radical].

    PubMed

    Dou, Jian; Hua, Lei; Hou, Ke-Yong; Jiang, Lei; Xie, Yuan-Yuan; Zhao, Wu-Duo; Chen, Ping; Wang, Wei-Guo; Di, Tian; Li, Hai-Yang

    2014-05-01

    A home-made chemical ionization time-of-flight mass spectrometer (TOFMS) has been developed for continuous measurements of atmospheric hydroxyl radical. Based on the atmospheric pressure chemical ionization technique, an ionization source with orthogonal dual tube structure was adopted in the instrument, which minimized the interference between the reagent gas ionization and the titration reaction. A 63Ni radioactive source was fixed inside one of the orthogonal tubes to generate reactant ion of NO(-)(3) from HNO3 vapor. Hydroxyl radical was first titrated by excess SO2 to form equivalent concentrations of H2SO4 in the other orthogonal tube, and then reacted with NO(-)(3) ions in the chemical ionization chamber, leading to HSO(-)(4) formation. The concentration of atmospheric hydroxyl radical can be directly calculated by measuring the intensities of the HSOj product ions and the NO(-)(3) reactant ions. The analytical capability of the instrument was demonstrated by measuring hydroxyl radical in laboratory air, and the concentration of the hydroxyl radical in the investigated air was calculated to be 1.6 x 106 molecules*cm ', based on 5 seconds integration. The results have shown that the instrument is competent for in situ continuous measurements of atmospheric trace radical. PMID:25055654

  18. High-precision determination of osmium and rhenium isotope ratios by in situ oxygen isotope ratio correction using negative thermal ionization mass spectrometry

    Microsoft Academic Search

    Yongzhong Liu; Min Huang; Akimasa Masuda; Masao Inoue

    1998-01-01

    The Os and Re isotope ratios were determined from the measurements of OsO3 and ReO4? ions by negative thermal ionization mass spectrometry. It was found that the oxygen isotope ratios of OsO3? and ReO4 ions vary to a large extent by the fluctuations in oxygen pressure in the ion source of the mass spectrometer and that the stability of oxygen

  19. Evaluation of matrix-assisted laser desorption ionization-time-of-flight mass spectrometry for species identification of Nonfermenting Gram-Negative Bacilli.

    PubMed

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

    2015-05-01

    Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) to identify 396 Nonfermenting Gram-Negative Bacilli clinical isolates was evaluated in comparison with conventional phenotypic tests and/or molecular methods. MALDI-TOF MS identified to species level 256 isolates and to genus or complex level 112 isolates. It identified 29 genera including uncommon species. PMID:25765149

  20. Soft Ionization of Saturated Hydrocarbons, Alcohols and Nonpolar Compounds by Negative-Ion Direct Analysis in Real-Time Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Cody, Robert B.; Dane, A. John

    2013-03-01

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

  1. An iodide-adduct high-resolution time-of-flight chemical-ionization mass spectrometer: application to atmospheric inorganic and organic compounds.

    PubMed

    Lee, Ben H; Lopez-Hilfiker, Felipe D; Mohr, Claudia; Kurtén, Theo; Worsnop, Douglas R; Thornton, Joel A

    2014-06-01

    A high-resolution time-of-flight chemical-ionization mass spectrometer (HR-ToF-CIMS) using Iodide-adducts has been characterized and deployed in several laboratory and field studies to measure a suite of organic and inorganic atmospheric species. The large negative mass defect of Iodide, combined with soft ionization and the high mass-accuracy (<20 ppm) and mass-resolving power (R>5500) of the time-of-flight mass spectrometer, provides an additional degree of separation and allows for the determination of elemental compositions for the vast majority of detected ions. Laboratory characterization reveals Iodide-adduct ionization generally exhibits increasing sensitivity toward more polar or acidic volatile organic compounds. Simultaneous retrieval of a wide range of mass-to-charge ratios (m/Q from 25 to 625 Th) at a high frequency (>1 Hz) provides a comprehensive view of atmospheric oxidative chemistry, particularly when sampling rapidly evolving plumes from fast moving platforms like an aircraft. We present the sampling protocol, detection limits and observations from the first aircraft deployment for an instrument of this type, which took place aboard the NOAA WP-3D aircraft during the Southeast Nexus (SENEX) 2013 field campaign. PMID:24800638

  2. Monitoring of antifouling agents in water samples by on-line solid-phase extraction-liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Gimeno, R A; Aguilar, C; Marcé, R M; Borrull, F

    2001-04-27

    An automatic method for determining diuron, irgarol 1051, folpet and dichlofluanid in seawater samples have been developed. This method is based on the on-line coupling of solid-phase extraction (SPE) with a highly crosslinked polymeric sorbent, LiChrolut EN, to liquid chromatography followed by atmospheric pressure chemical ionization (APCI) and mass spectrometry. The operational parameters affecting the APCI interface have been studied in both positive and negative ionization modes. The use of LiChrolut EN in the SPE produced recoveries of over 85% for all the compounds when 100 ml of seawater sample was preconcentrated. Calibration was carried out in both ionization modes and in full-scan and selected-ion monitoring (SIM). The method allowed all the analytes to be detected at 5 ng l(-1) in SIM acquisition mode except folpet, which, because of its low response, could only be detected at 250 ng l(-1). The method was used to analyse water samples taken from five different marina and fishing ports along the coast of Tarragona, Catalonia (Spain), over a 5-month period. Diuron and irgarol 1051 were detected and quantified in most samples at concentration levels ranging from 27 to 420 ng l(-1) for diuron and from 15 to 511 ng l(-1) for irgarol 1051. PMID:11358242

  3. Modeling of plasma chemical processes in the artificial ionized layer in the upper atmosphere by the nanosecond corona discharge

    Microsoft Academic Search

    A. L. Vikharev; A. M. Gorbachev; O. A. Ivanov; A. L. Kolisko; A. G. Litvak

    1993-01-01

    The plasma chemical processes in the corona discharge formed in air by a series of high voltage pulses of nanosecond duration are investigated experimentally. The experimental conditions (reduced electric field, duration and repetition frequency of the pulses, gas pressure in the chamber) modeled the regime of creation of the artificial ionized layer (AIL) in the upper atmosphere by a nanosecond

  4. Rare earth oxide catalyzed oxidation of rhenium to ReO/sub 4//sup -/ and ReO/sub 3//sup -/ as observed by negative surface ionization mass spectrometry

    SciTech Connect

    Delmore, J.E.

    1987-05-21

    A surface ionization mass spectrometer was used to observe the in situ formation of ReO/sub 4//sup -/ and ReO/sub 3//sup -/ gas-phase ions resulting from the rare earth oxide catalyzed reaction of water with metallic rhenium. Water was found to be 6-10-fold more efficient than oxygen as an oxidizer at temperatures around 1100/sup 0/C. Normal, oxygen-18 enriched, and deuteriated water were used to elucidate the oxidation mechanism. The results were consistent with a mechanism whereby the rare earth oxide goes through a stoichiometric cycle, with the highly stoichiometric oxide functioning as a strong oxidizer and the oxidizing potential being reduced as the rare earth moves into a mixed valency state with reduced oxygen content. The oxygen stoichiometry (and the oxidative potential) is then restored by reaction with water. The oxygen of the water is slowly equilibrated with the original oxygen of the rare earth oxide, with the variations between the rare earths being consistent with known rare earth mixed valency chemistry. The highly stoichiometric oxide readily oxidizes rhenium with high efficiency. The results of this work suggest that both positive and negative surface ionization mass spectromery should be explored as tools for the in situ study of surface catalyzed gas-solid reactions. Few techniques are capable of monitoring the dynamics of solid-state chemical reactions at these temperatures, and surface ionization appears to offer some hope for elucidating at least some reactions at elevated temperatures.

  5. Calibrated In Situ Measurement of UT/LS Water Vapor Using Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Thornberry, T. D.; Rollins, A.; Gao, R.; Watts, L. A.; Ciciora, S. J.; McLaughlin, R. J.; Fahey, D. W.

    2011-12-01

    Over the past several decades there has been considerable disagreement among in situ water vapor measurements by different instruments at the low part per million (ppm) mixing ratios found in the upper troposphere and lower stratosphere (UT/LS). These discrepancies contribute to uncertainty in our understanding of the microphysics related to cirrus cloud particle nucleation and growth and affect our ability to determine the effect of climate changes on the radiatively important feedback from UT/LS water vapor. To address the discrepancies observed in measured UT/LS water vapor, a new chemical ionization mass spectrometer (CIMS) instrument has been developed for the fast, precise, and accurate measurement of water vapor at low mixing ratios. The instrument utilizes a radioactive ? particle source to ionize a flow of sample air drawn into the instrument. A cascade of ion-molecule reactions results in the production of protonated water ions proportional to the water vapor mixing ratio that are then detected by the mass spectrometer. The multi-step nature of the ionization mechanism results in a non-linear sensitivity to water vapor, necessitating calibration across the full range of values to be measured. To accomplish this calibration, we have developed a novel calibration scheme using catalytic oxidation of hydrogen to produce well-defined water vapor mixing ratios that can be introduced into the instrument inlet during flight. The CIMS instrument was deployed for the first time aboard the NASA WB-57 high altitude research aircraft during the Mid-latitude Airborne Cirrus Properties Experiment (MACPEX) mission in March and April 2011. The sensitivity of the instrument to water vapor was calibrated every ~45 minutes in flight from < 1 to 150 ppm. Analysis of in-flight data demonstrates a typical sensitivity of 2000 Hz/ppm at 4.5 ppm with a signal to noise ratio (2 ?) > 50 for a 1 second measurement. The instrument and its calibration system performed successfully in 7 flights during the MACPEX mission, sampling water vapor mixing ratios as low as 4 ppm in stratospheric air. A comparison of the new measurement with other measurements on board the aircraft is expected to help resolve the long-standing differences in low water measurements in the lower stratosphere.

  6. Production and Utilization of CO3- Produced by a Corona Discharge in Air for Atmospheric Pressure Chemical Ionization

    SciTech Connect

    Ewing, Robert G.; Waltman, Melanie J.

    2010-12-14

    Atmospheric pressure chemical ionization is a multistep ionization process used in mass spectrometry and ion mobility spectrometry. The formation of product ions depends upon interactions with the analyte and the reactant ion species formed in the ionization source. The predominant reactant ion observed in a point-to-plane corona discharge in air occurs at m/z 60. There have been multiple references in the literature to the identity of this ion with some disagreement. It was postulated to be either CO3- or N2O2-. The identity of this ion is important as it is a key to the ionization of analytes. It was determined here to be CO3- through the use of 18O labeled oxygen. Further confirmation was provided through MS/MS studies. The ionization of nitroglycerine (NG) with CO3- produced the adduct NG•CO3-. This was compared to ionization with NO3- and Cl- reactant ions that also formed adducts with NG. The fragmentation patterns of these three adducts provides insight into the charge distribution and indicates that CO3- has a relatively high electron affinity similar to that of nitrate.

  7. 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.

  8. 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

  9. 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.

  10. Negative-tone block copolymer lithography by in situ surface chemical modification.

    PubMed

    Kim, Bong Hoon; Byeon, Kyeong-Jae; Kim, Ju Young; Kim, Jinseung; Jin, Hyeong Min; Cho, Joong-Yeon; Jeong, Seong-Jun; Shin, Jonghwa; Lee, Heon; Kim, Sang Ouk

    2014-10-29

    Negative-tone block copolymer (BCP) lithography based on in situ surface chemical modification is introduced as a highly efficient, versatile self-assembled nanopatterning. BCP blends films consisting of end-functionalized low molecular weight poly(styrene-ran-methyl methacrylate) and polystyrene-block-Poly(methyl methacylate) can produce surface vertical BCP nanodomains on various substrates without prior surface chemical treatment. Simple oxygen plasma treatment is employed to activate surface functional group formation at various substrates, where the end-functionalized polymers can be covalently bonded during the thermal annealing of BCP thin films. The covalently bonded brush layer mediates neutral interfacial condition for vertical BCP nanodomain alignment. This straightforward approach for high aspect ratio, vertical self-assembled nanodomain formation facilitates single step, site-specific BCP nanopatterning widely useful for various substrates. Moreover, this approach is compatible with directed self-assembly approaches to produce device oriented laterally ordered nanopatterns. PMID:24912807

  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. Estrogen mimics induce genes encoding chemical efflux proteins in gram-negative bacteria.

    PubMed

    Li, Xinhua; Teske, Sondra; Conroy-Ben, Otakuye

    2015-06-01

    Escherichia coli and Pseudomonas aeruginosa are gram-negative bacteria found in wastewater and biosolids. Spanning the inner and outer membrane are resistance-nodulation-cell division superfamily (RND) efflux pumps responsible for detoxification of the cell, typically in response to antibiotics and other toxicity inducing substrates. Here, we show that estrogenic endocrine disruptors, common wastewater pollutants, induce genes encoding chemical efflux proteins. Bacteria were exposed to environmental concentrations of the synthetic estrogen 17?-ethynylestradiol, the surfactant nonylphenol, and the plasticizer bisphenol-A, and analyzed for RND gene expression via q-PCR. Results showed that the genes acrB and yhiV were over-expressed in response to the three chemicals in E. coli, and support previous findings that these two transporters export hormones. P. aeruginosa contains 12 RND efflux pumps, which were differentially expressed in response to the three chemicals: 17?-ethynylestradiol, bisphenol-A, and nonylphenol up-regulated mexD and mexF, while nonylphenol and bisphenol-A positively affected transcription of mexK, mexW, and triC. Gene expression via q-PCR of RND genes may be used to predict the interaction of estrogen mimics with RND genes. One bacterial response to estrogen mimic exposure is to induce gene expression of chemical efflux proteins, which leads to the expulsion of the contaminant from the cell. PMID:25754012

  13. Ionization controls for biomineralization-inspired CO2 chemical looping at constant room temperature.

    PubMed

    Liu, Zhaoming; Hu, Yadong; Zhao, Hongqing; Wang, Yang; Xu, Xurong; Pan, Haihua; Tang, Ruikang

    2015-04-01

    Living organisms such as corals can carry out CO2 looping efficiently via biomineralization under ambient conditions. Inspired by this natural process, we establish a solution system of calcium acetate-ethanol-water (Ca(Ac)2-C2H5OH-H2O) for CO2 chemical looping at constant room temperature. The CO2 capture is achieved by its reaction with Ca(Ac)2 to form calcium carbonate (CaCO3) mineral and HAc in the binary solvent with a high C2H5OH content. However, an increase in the H2O content in the system triggers acetic acid (HAc)-induced CaCO3 dissolution to release CO2. The system can be recovered for CO2 capture readily by the replenishment of C2H5OH. This biomimetic mineralization-based CO2 capture/release is controlled by the ionization states of the electrolytes, and is precisely regulated in the C2H5OH-H2O binary solvent. Our attempt highlights the fundamental principle of solution chemistry in reaction control and provides a bioinspired strategy for CO2 capture/release with very low cost and easy availability. PMID:25787086

  14. Document authentication at molecular levels using desorption atmospheric pressure chemical ionization mass spectrometry imaging.

    PubMed

    Li, Ming; Jia, Bin; Ding, Liying; Hong, Feng; Ouyang, Yongzhong; Chen, Rui; Zhou, Shumin; Chen, Huanwen; Fang, Xiang

    2013-09-01

    Molecular images of documents were obtained by sequentially scanning the surface of the document using desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS), which was operated in either a gasless, solvent-free or methanol vapor-assisted mode. The decay process of the ink used for handwriting was monitored by following the signal intensities recorded by DAPCI-MS. Handwritings made using four types of inks on four kinds of paper surfaces were tested. By studying the dynamic decay of the inks, DAPCI-MS imaging differentiated a 10-min old from two 4 h old samples. Non-destructive forensic analysis of forged signatures either handwritten or computer-assisted was achieved according to the difference of the contour in DAPCI images, which was attributed to the strength personalized by different writers. Distinction of the order of writing/stamping on documents and detection of illegal printings were accomplished with a spatial resolution of about 140 µm. A Matlab® written program was developed to facilitate the visualization of the similarity between signature images obtained by DAPCI-MS. The experimental results show that DAPCI-MS imaging provides rich information at the molecular level and thus can be used for the reliable document analysis in forensic applications. PMID:24078245

  15. 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

  16. Ion mobility spectrometric analysis of vaporous chemical warfare agents by the instrument with corona discharge ionization ammonia dopant ambient temperature operation.

    PubMed

    Satoh, Takafumi; Kishi, Shintaro; Nagashima, Hisayuki; Tachikawa, Masumi; Kanamori-Kataoka, Mieko; Nakagawa, Takao; Kitagawa, Nobuyoshi; Tokita, Kenichi; Yamamoto, Soichiro; Seto, Yasuo

    2015-03-20

    The ion mobility behavior of nineteen chemical warfare agents (7 nerve gases, 5 blister agents, 2 lachrymators, 2 blood agents, 3 choking agents) and related compounds including simulants (8 agents) and organic solvents (39) was comparably investigated by the ion mobility spectrometry instrument utilizing weak electric field linear drift tube with corona discharge ionization, ammonia doping, purified inner air drift flow circulation operated at ambient temperature and pressure. Three alkyl methylphosphonofluoridates, tabun, and four organophosphorus simulants gave the intense characteristic positive monomer-derived ion peaks and small dimer-derived ion peaks, and the later ion peaks were increased with the vapor concentrations. VX, RVX and tabun gave both characteristic positive monomer-derived ions and degradation product ions. Nitrogen mustards gave the intense characteristic positive ion peaks, and in addition distinctive negative ion peak appeared from HN3. Mustard gas, lewisite 1, o-chlorobenzylidenemalononitrile and 2-mercaptoethanol gave the characteristic negative ion peaks. Methylphosphonyl difluoride, 2-chloroacetophenone and 1,4-thioxane gave the characteristic ion peaks both in the positive and negative ion mode. 2-Chloroethylethylsulfide and allylisothiocyanate gave weak ion peaks. The marker ion peaks derived from two blood agents and three choking agents were very close to the reactant ion peak in negative ion mode and the respective reduced ion mobility was fluctuated. The reduced ion mobility of the CWA monomer-derived peaks were positively correlated with molecular masses among structurally similar agents such as G-type nerve gases and organophosphorus simulants; V-type nerve gases and nitrogen mustards. The slope values of the calibration plots of the peak heights of the characteristic marker ions versus the vapor concentrations are related to the detection sensitivity, and within chemical warfare agents examined the slope values for sarin, soman, tabun and nitrogen mustards were higher. Some CWA simulants and organic solvents gave the ion peaks eluting at the similar positions of the CWAs, resulting in false positive alarms. PMID:25732583

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

    Microsoft Academic Search

    Mikio Yashiki; Tohru Kojima; Tetsuji Miyazaki; Nobuyuki Nagasawa; Yasumasa Iwasaki; Kenji Hara

    1995-01-01

    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 ion monitoring. A vial containing a urine sample potassium carbonate and pentadeuterated methamphetamine which was used as an internal standard was heated at 80 °C for 20 min. The needle

  18. Qualitative analysis of some carboxylic acids by ion-exclusion chromatography with atmospheric pressure chemical ionization mass spectrometric detection

    Microsoft Academic Search

    Murad I. H. Helaleh; Kazuhiko Tanaka; Hiroshi Taoda; Wenzhi Hu; Kiyoshi Hasebe; Paul R. Haddad

    2002-01-01

    A simple, selective and sensitive method for the determination of carboxylic acids has been developed. A mixture of formic, acetic, propionic, valeric, isovaleric, isobutyric, and isocaproic acids has been separated on a polymethacrylate-based weak acidic cation-exchange resin (TSK gel OA pak-A) based on an ion-exclusion chromatographic mechanism with detection using UV-photodiode array, conductivity and atmospheric pressure chemical ionization mass spectrometry

  19. 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)

  20. 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

  1. 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.

  2. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol - a laboratory and field study

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Brüggemann, M.; Ehn, M.; Junninen, H.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2013-02-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft-ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was improved by a factor of 7.5 to 11 (e.g. ∼40 ng m3 for pinonic acid) by using the miniature versatile aerosol concentration enrichment system (mVACES) upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards - pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total submicron organic aerosol mass was estimated to be about 60%, based on the response of pinic acid. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94) demonstrates soft-ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (?-pinene and ?3-carene) cannot account for all of the measured fragments. Possible explanations for those unaccounted fragments are the presence of unidentified or underestimated biogenic SOA precursors, or that different products are formed by a different oxidant mixture of the ambient air compared to the chamber ozonolysis.

  3. Single-Photon Multiple Detachment in Fullerene Negative Ions: Absolute Ionization Cross Sections and the Role of the Extra Electron

    NASA Astrophysics Data System (ADS)

    Bilodeau, R. C.; Gibson, N. D.; Walter, C. W.; Esteves-Macaluso, D. A.; Schippers, S.; Müller, A.; Phaneuf, R. A.; Aguilar, A.; Hoener, M.; Rost, J. M.; Berrah, N.

    2013-07-01

    We have obtained experimental photo-double- and photo-triple-detachment cross sections for the fullerene negative ion using Advanced Light Source photons of 17-90 eV. The cross sections are 2 and 2.5 times larger than those for C60 and appear to be compressed and shifted in photon energy as compared to C60. Our analysis reveals that the additional electron in C60- primarily produces screening which is responsible for the modification of the spectrum. Both screening effects, the shift and the compression, can be quantitatively accounted for by a linear transformation of the energy axis. Applying the transformation allows us to map the neutral and negative ion cross sections onto each other, pointing out the close relationship of correlated few-electron dynamics in neutral and negatively charged extended systems. In contrast, dynamics of neutral and negatively charged atoms or small molecules are typically not closely related.

  4. Cyclic acyloxonium ions as diagnostic aids in the characterization of chloropropanol esters under electron impact (EI), electrospray ionization (ESI), and atmospheric pressure chemical ionization (APCI) conditions.

    PubMed

    Rahn, Anja K K; Yaylayan, Varoujan A

    2013-06-26

    During mass spectrometric analysis of various lipids and lipid derivatives such as the chlorinated counterparts of triacylglycerols, the detailed structure of the characteristic and common ions formed under electron impact (EI), electrospray ionization (ESI), and atmospheric pressure chemical ionization (APCI) conditions by the loss of a single fatty acid remains ambiguous. These ions are designated in the literature as "diacylglyceride ions" and are frequently depicted with a molecular formula without showing any structural features and sometimes represented as cyclic acyloxonium ions. Characterization of these ions is of considerable importance due to their utility in structural identification of lipid derivatives. This study provides complementary evidence on the cyclic nature of "diacylglyceride ions" through the use of the simplest 3-monochloropropanediol diester as a model and the use of isotope labeling technique. Tandem MS/MS studies have indicated that the ion at m/z 135.6 generated from 1,2-bis(acetoyl)-3-chloropropane through the loss of an acetyl group was identical to the ion at m/z 135.6 generated from 4-chloromethyl-2,2-dimethyl-1,3-dioxolane, the latter being generated from a cyclic precursor through the loss of a methyl radical, keeping the dioxolane ring structure intact, thus confirming the cyclic nature of these ions. The corresponding cyclic oxonium ions generated from longer chain chloropropanol diesters, such as the ion at m/z 331.2 originating from 3-monochloropropanediol (3-MCPD) diesters containing palmitic acid(s), could serve as chemical markers for the presence chloropropanol esters. PMID:23734847

  5. High-performance liquid chromatography/high-resolution multiple stage tandem mass spectrometry using negative-ion-mode hydroxide-doped electrospray ionization for the characterization of lignin degradation products.

    PubMed

    Owen, Benjamin C; Haupert, Laura J; Jarrell, Tiffany M; Marcum, Christopher L; Parsell, Trenton H; Abu-Omar, Mahdi M; Bozell, Joseph J; Black, Stuart K; Kenttämaa, Hilkka I

    2012-07-17

    In the search for a replacement for fossil fuel and the valuable chemicals currently obtained from crude oil, lignocellulosic biomass has become a promising candidate as an alternative biorenewable source for crude oil. Hence, many research efforts focus on the extraction, degradation, and catalytic transformation of lignin, hemicellulose, and cellulose. Unfortunately, these processes result in the production of very complex mixtures. Further, while methods have been developed for the analysis of mixtures of oligosaccharides, this is not true for the complex mixtures generated upon degradation of lignin. For example, high-performance liquid chromatography/multiple stage tandem mass spectrometry (HPLC/MS(n)), a tool proven to be invaluable in the analysis of complex mixtures derived from many other biopolymers, such as proteins and DNA, has not been implemented for lignin degradation products. In this study, we have developed an HPLC separation method for lignin degradation products that is amenable to negative-ion-mode electrospray ionization (ESI doped with NaOH), the best method identified thus far for ionization of lignin-related model compounds without fragmentation. The separated and ionized compounds are then analyzed by MS(3) experiments to obtain detailed structural information while simultaneously performing high-resolution measurements to determine their elemental compositions in the two parts of a commercial linear quadrupole ion trap/Fourier-transform ion cyclotron resonance mass spectrometer. A lignin degradation product mixture was analyzed using this method, and molecular structures were proposed for some components. This methodology significantly improves the ability to analyze complex product mixtures that result from degraded lignin. PMID:22746183

  6. 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

  7. Comparison of electrospray ionization and atmospheric pressure chemical ionization for multi-residue analysis of biocides, UV-filters and benzothiazoles in aqueous matrices and activated sludge by liquid chromatography-tandem mass spectrometry.

    PubMed

    Wick, Arne; Fink, Guido; Ternes, Thomas A

    2010-04-01

    This paper describes the development of a multi-residue method for the determination of 36 emerging organic pollutants (26 biocides, 5 UV-filters and 5 benzothiazoles) in raw and treated wastewater, activated sludge and surface water using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The target analytes were enriched from water samples adjusted to pH 6 by solid-phase extraction (SPE) on Oasis HLB 200mg cartridges and eluted with a mixture of methanol and acetone (60/40, v/v). Extraction of freeze-dried sludge samples was accomplished by pressurized liquid extraction (PLE) using a mixture of methanol and water (50/50, v/v) as extraction solvent followed by SPE. LC-tandem MS detection was compared using electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) in positive and negative ionization mode. ESI exhibited strong ion suppression for most target analytes, while APCI was generally less susceptible to ion suppression but partially leading to ion enhancement of up to a factor of 10. In general, matrix effects could be compensated using stable isotope-labeled surrogate standards, indicated by relative recoveries ranging from 70% to 130%. In wastewater, activated sludge and surface water up to 33 analytes were detected. Maximum concentrations up to 5.1 and 3.9mugL(-1) were found in raw wastewater for the water-soluble UV-filters benzophenone-4 (BZP-4) and phenylbenz-imidazole sulfonic acid (PBSA), respectively. For the first time, the anti-dandruff climbazole was detected in raw wastewater and in activated sludge with concentrations as high as 1.4 microg L(-1) and 1.2 microg gTSS(-1), respectively. Activated sludge is obviously a sink for four benzothiazoles and two isothiazolones, as concentrations were detected in activated sludge between 120 ng gTSS(-1) (2-n-octyl-4-isothiazolin-3-one, OIT) to 330 ng gTSS(-1) (benzothiazole-2-sulfonic acid, BTSA). PMID:20202641

  8. Plasma chemical model for decomposition of SF6 in a negative glow corona discharge

    NASA Astrophysics Data System (ADS)

    van Brunt, R. J.; Herron, J. T.

    1994-01-01

    A zonal plasma chemical model is proposed to account for the observed oxidation and decomposition of sulfur hexafluoride (SF6) by a negative, point-to-plane glow-type corona discharge in pressurized SF6/O2/H2O gas mixtures. The model yields dependencies of stable neutral oxidation by-products such as SOF2, SO2F2, SOF4, S2F10, and SO2 on time, discharge current, and O2 and H2O concentrations which are consistent with measured results. Electron-impact-induced dissociation of SF6 in the glow region of the discharge is the decomposition rate-controlling process. The relative roles played by different reactions involving neutral free radicals and ions in different zones of the discharge are examined, and in some cases, reaction rate coefficients have been adjusted within reasonable limits to give best fits to observed production rates of various by-products. Problems of uniqueness that arise because of gaps in our knowledge about important processes that should be included in the model are also discussed.

  9. Adhesion-dependent negative friction coefficient on chemically modified graphite at the nanoscale.

    PubMed

    Deng, Zhao; Smolyanitsky, Alex; Li, Qunyang; Feng, Xi-Qiao; Cannara, Rachel J

    2012-12-01

    From the early tribological studies of Leonardo da Vinci to Amontons' law, friction has been shown to increase with increasing normal load. This trend continues to hold at the nanoscale, where friction can vary nonlinearly with normal load. Here we present nanoscale friction force microscopy (FFM) experiments for a nanoscale probe tip sliding on a chemically modified graphite surface in an atomic force microscope (AFM). Our results demonstrate that, when adhesion between the AFM tip and surface is enhanced relative to the exfoliation energy of graphite, friction can increase as the load decreases under tip retraction. This leads to the emergence of an effectively negative coefficient of friction in the low-load regime. We show that the magnitude of this coefficient depends on the ratio of tip-sample adhesion to the exfoliation energy of graphite. Through both atomistic- and continuum-based simulations, we attribute this unusual phenomenon to a reversible partial delamination of the topmost atomic layers, which then mimic few- to single-layer graphene. Lifting of these layers with the AFM tip leads to greater deformability of the surface with decreasing applied load. This discovery suggests that the lamellar nature of graphite yields nanoscale tribological properties outside the predictive capacity of existing continuum mechanical models. PMID:23064494

  10. No-discharge atmospheric pressure chemical ionization: evaluation and application to the analysis of animal drug residues in complex matrices.

    PubMed

    Turnipseed, Sherri B; Andersen, Wendy C; Karbiwnyk, Christine M; Roybal, José E; Miller, Keith E

    2006-01-01

    Alternative ionization methods are increasingly being utilized to increase the versatility and selectivity of liquid chromatography/mass spectrometry (LC/MS). One such technique is the practice of using commercially available atmospheric pressure chemical ionization (APCI) sources with the corona discharge turned off, a process termed no-discharge APCI (ND-APCI). The relative LC/MS responses for several different classes of veterinary drugs were obtained by using ND-APCI, electrospray ionization (ESI), and APCI. While the ND-APCI-MS and -MSn spectra for these compounds were comparable with ESI, ND-APCI provided advantages in sensitivity and selectivity for some compounds. Drugs that were charged in solution as cations or sodium adducts responded particularly well with this technique. Instrumental parameters such as temperatures, gas and liquid flow rates, and source design were investigated to determine their effect on the process of ND-APCI. This paper explores advantages of using ND-APCI for the determination and confirmation of drug residues that might be found in food matrices, including malachite green residues in fish tissue and avermectin residues in milk. PMID:16541409

  11. Evaluation of gas chromatography-atmospheric pressure chemical ionization-mass spectrometry as an alternative to gas chromatography-electron ionization-mass spectrometry: avocado fruit as example.

    PubMed

    Hurtado-Fernández, Elena; Pacchiarotta, Tiziana; Longueira-Suárez, Enrique; Mayboroda, Oleg A; Fernández-Gutiérrez, Alberto; Carrasco-Pancorbo, Alegría

    2013-10-25

    Although GC-APCI-MS was developed more than 40 years ago this coupling is still far from being a routine technique. One of the reasons explaining the limited use of GC-APCI so far is the lack of spectral database which facilitates the identification of the compounds under study. The first application of a very recently developed GC-APCI database to identify as many compounds as possible in a complex matrix such as avocado fruit is presented here. The results achieved by using this database has been checked against those obtained using traditional GC-EI-MS and a comparison of the MS signals observed in both ionization sources has been carried out. 100 compounds belonging to different chemical families were identified in the matrix under study. Considering the results of this study, the wide range of application (in terms of polarity and size of analytes) and the robustness of APCI as interface, the high quality of TOF spectra, and our library as a publicly available resource, GC-APCI-TOF MS is definitively a valuable addition to the "metabolomics toolbox". PMID:24054422

  12. Synergistic effect of ionizing radiation on chemical disinfectant treatments for reduction of natural microflora on seafood

    NASA Astrophysics Data System (ADS)

    Kim, Hyunjoo; Ha, Ji-Hyoung; Lee, Ju-Woon; Jo, Cheorun; Ha, Sang-Do

    2012-08-01

    The purpose of this study was to determine whether combined treatments would produce synergistic disinfection effects on seafood products such as mussel and squid compared with single treatments. We investigated the bactericidal effects of chlorine and ionizing radiation on the natural microflora of mussel and squid. Total aerobic bacteria initially ranged from 102 to 104 Log CFU/g. More than 100 ppm of chlorine and irradiation at 1 kGy were sufficient to reduce the total aerobic bacteria on mussel and squid to a level lower than detection limit (10 CFU/g). Synergistic effects against natural microflora were observed for all combined treatment. These results suggest that a significant synergistic benefit results from combine chlorine-ionizing radiation treatment against natural microflora on mussel and squid.

  13. Scanning Diode Laser Desorption Thin-Layer Chromatography Coupled with Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Peng, Song; Ahlmann, Norman; Edler, Michael; Franzke, Joachim

    Continuous wave diode laser is applied for desorption of an analyte from a porous surface of a thin-layer plate covered with a graphite suspension. The thermally desorbed analyte molecules are ionized in the gas phase by a corona discharge at atmospheric pressure. Therefore, both essential processes - the desorption and the ionization of analyte molecules, which are often performed in one step - are separated. Reserpine was chosen as model analyte, which is often used for specification of mass spectrometers. No fragmentation was observed because of efficient collisional cooling under atmospheric pressure. The influence of diode laser power and the composition of the graphite suspension were investigated, and a primary optimization was performed. An interface to allow online qualitative and quantitative full plate detection and analysis of compounds separated by thin-layer chromatography is presented.

  14. Simultaneous determination of hair cortisol, cortisone and DHEAS with liquid chromatography-electrospray ionization-tandem mass spectrometry in negative mode.

    PubMed

    Chen, Zheng; Li, Jifeng; Zhang, Jing; Xing, Xue; Gao, Wei; Lu, Zuhong; Deng, Huihua

    2013-06-15

    The present study aimed to develop a novel method for simultaneous assay of cortisol, cortisone and dehydroepiandrosterone sulfate (DHEAS) in human hair. The method was based on liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-MS/MS) in negative mode. Analytes were extracted from 20-mg hair incubated in 1ml of methanol for 5 days. 100?l non-SPE supernatant of the incubation solution was utilized in LC-MS/MS analysis. The liquid chromatography separation was performed on a reversed-phase C18 column with a mobile phase of 80:20 (v:v) methanol and deionized water containing 0.1% formic acid. The use of ESI in negative mode and the use of a small volume of the incubation solution significantly improved assay sensitivity. The linear range was 5-250pg/mg for cortisol and cortisone, and 5-500pg/mg for DHEAS. The limit of detection was 2pg/mg for the three analytes in hair. The coefficients of variation for intra-day and inter-day assay were less than 10%. The method was applied to determine the three analytes mentioned above of hair samples from 103 participants. The results indicated that there was no significant effect of age and education level on the hair cortisol, cortisone and DHEAS levels. The simple treatment procedure developed in the present study may facilitate simultaneous measurement of more steroids in hair. PMID:23685429

  15. The ionized gas in the central region of NGC 5253. 2D mapping of the physical and chemical properties

    NASA Astrophysics Data System (ADS)

    Monreal-Ibero, A.; Walsh, J. R.; Vílchez, J. M.

    2012-08-01

    Context. Blue compact dwarf (BCD) galaxies constitute the ideal laboratories to test the interplay between massive star formation and the surrounding gas. As one of the nearest BCD galaxies, NGC 5253 was previously studied with the aim to elucidate in detail the starburst interaction processes. Some open issues regarding the properties of its ionized gas still remain to be addressed. Aims: The 2D structure of the main physical and chemical properties of the ionized gas in the core of NGC 5253 has been studied. Methods: Optical integral field spectroscopy (IFS) data has been obtained with FLAMES Argus and lower resolution gratings of the Giraffe spectrograph. Results: We derived 2D maps for different tracers of electron density (ne), electron temperature (Te) and ionization degree. The maps for ne as traced by [O ii], [S ii], [Fe iii], and [Ar iv] line ratios are compatible with a 3D stratified view of the nebula with the highest ne in the innermost layers and a decrease of ne outwards. 2D maps of Te were measured from [O iii] and [S ii] line ratios; to our knowledge, this is the first time that a Te map based on [S ii] lines for an extragalactic object has been presented. The joint interpretation of the Te([S ii]) and Te([O iii]) maps is consistent with a Te structure in 3D with higher temperatures close to the main ionizing source surrounded by a colder and more diffuse component. The highest ionization degree is found at the peak of emission for the gas with relatively high ionization in the main Giant H ii Region and lower ionization degree delineating the more extended diffuse component. We derived abundances of oxygen, neon, argon, and nitrogen. Abundances for O, Ne and Ar are constant over the mapped area within ?0.1 dex. The mean 12 + log (O/H) is 8.26 ± 0.04 while the relative abundances of log (N/O), log (Ne/O) and log (Ar/O) were ~-1.32 ± 0.05, -0.65 ± 0.03 and -2.33 ± 0.06, respectively. There are two locations with enhanced N/O. The first (log (N/O) ~ -0.95) occupies an area of about 80 pc × 35 pc and is associated to two super star clusters. The second (log (N/O) ~ -1.17), reported here for the first time, is associated to two moderately massive (2-4 × 104 M?) and relatively old (~10 Myr) clusters. A comparison of the N/O map with those produced by strong line methods supports the use of N2O2 over N2S2 in the search for chemical inhomogeneities within a galaxy. The results on the localized nitrogen enhancement were used to compile and discuss the factors that affect the complex relationship between Wolf-Rayet stars and N/O excess. Based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere, Chile (ESO Programme 078.B-0043 and 383.B-0043).

  16. Matrix-assisted laser desorption ionization-time of flight mass spectrometry for identification of nonfermenting gram-negative bacilli isolated from cystic fibrosis patients.

    PubMed

    Degand, Nicolas; Carbonnelle, Etienne; Dauphin, Brunhilde; Beretti, Jean-Luc; Le Bourgeois, Muriel; Sermet-Gaudelus, Isabelle; Segonds, Christine; Berche, Patrick; Nassif, Xavier; Ferroni, Agnès

    2008-10-01

    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 identification of these bacteria. A set of reference strains belonging to 58 species of clinically relevant nonfermenting gram-negative bacilli was used. To identify peaks discriminating between these various species, the profile of 10 isolated colonies obtained from 10 different passages was analyzed for each referenced strain. Conserved peaks with a relative intensity greater than 0.1 were retained. The spectra of 559 clinical isolates were then compared to that of each of the 58 reference strains as follows: 400 Pseudomonas aeruginosa, 54 Achromobacter xylosoxidans, 32 Stenotrophomonas maltophilia, 52 Burkholderia cepacia complex (BCC), 1 Burkholderia gladioli, 14 Ralstonia mannitolilytica, 2 Ralstonia pickettii, 1 Bordetella hinzii, 1 Inquilinus limosus, 1 Cupriavidus respiraculi, and 1 Burkholderia thailandensis. Using this database, 549 strains were correctly identified. Nine BCC strains and one R. mannnitolilytica strain were identified as belonging to the appropriate genus but not the correct species. We subsequently engineered BCC- and Ralstonia-specific databases using additional reference strains. Using these databases, correct identification for these species increased from 83 to 98% and from 94 to 100% of cases, respectively. Altogether, these data demonstrate that, in CF patients, MALDI-TOF-MS is a powerful tool for rapid identification of nonfermenting gram-negative bacilli. PMID:18685005

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

    PubMed Central

    Degand, Nicolas; Carbonnelle, Etienne; Dauphin, Brunhilde; Beretti, Jean-Luc; Le Bourgeois, Muriel; Sermet-Gaudelus, Isabelle; Segonds, Christine; Berche, Patrick; Nassif, Xavier; Ferroni, Agnès

    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 identification of these bacteria. A set of reference strains belonging to 58 species of clinically relevant nonfermenting gram-negative bacilli was used. To identify peaks discriminating between these various species, the profile of 10 isolated colonies obtained from 10 different passages was analyzed for each referenced strain. Conserved peaks with a relative intensity greater than 0.1 were retained. The spectra of 559 clinical isolates were then compared to that of each of the 58 reference strains as follows: 400 Pseudomonas aeruginosa, 54 Achromobacter xylosoxidans, 32 Stenotrophomonas maltophilia, 52 Burkholderia cepacia complex (BCC), 1 Burkholderia gladioli, 14 Ralstonia mannitolilytica, 2 Ralstonia pickettii, 1 Bordetella hinzii, 1 Inquilinus limosus, 1 Cupriavidus respiraculi, and 1 Burkholderia thailandensis. Using this database, 549 strains were correctly identified. Nine BCC strains and one R. mannnitolilytica strain were identified as belonging to the appropriate genus but not the correct species. We subsequently engineered BCC- and Ralstonia-specific databases using additional reference strains. Using these databases, correct identification for these species increased from 83 to 98% and from 94 to 100% of cases, respectively. Altogether, these data demonstrate that, in CF patients, MALDI-TOF-MS is a powerful tool for rapid identification of nonfermenting gram-negative bacilli. PMID:18685005

  18. 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 solubility. Peanut hull bio-oil is much more compositionally complex and contains more nitrogen

  19. 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...

  20. 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

  1. Stability of plasma gamma-hydroxybutyrate determined by gas chromatography-positive ion chemical ionization-mass spectrometry.

    PubMed

    Chen, Meng; Andrenyak, David M; Moody, David E; Foltz, Rodger L

    2003-10-01

    An effective method for the determination of gamma-hydroxybutyric acid (GHB) in human plasma is described that utilizes a simple liquid-liquid extraction procedure and gas chromatography-positive ion chemical ionization-mass spectrometry (GC-PCI-MS). The method has been used to study the stability of plasma GHB under several storage conditions. Following the extraction with acetonitrile, GHB and deuterated GHB (GHB-d(6)) were derivatized with N,O-bis[trimethylsilyl] trifluoroacetamide (BSFTA). After the separation on a capillary GC column, the derivatives were ionized with ammonia reagent gas and analyzed by MS. The lower limit of quantitation in 100 microL of plasma was 2.5 microg/mL, over a range from 2.5 to 250 microg/mL. The coefficients of variation did not exceed 3.9% and the mean measured concentrations did not deviate more than 8% from the target for both intra- and interassay precision and accuracy. Plasma GHB was found to be stable at -20 degrees C for up to 9 months, at room temperature for 48 h, and after 3 freeze/thaw cycles. It was also found to be stable in processed samples stored at room temperature for 5 days and for 15 days at -20 degrees C. PMID:14606997

  2. Direct monitoring of chemical transformations by combining thin layer chromatography with nanoparticle-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Chen, Chun-Chi; Yang, Yung-Lin; Ou, Chun-Lin; Chou, Chih-Hung; Liaw, Chih-Chuang; Lin, Po-Chiao

    2013-03-01

    A nanomaterial-assisted method that combines thin layer chromatography (TLC) with matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) was developed to directly monitor chemical transformations. A substrate-dependent extraction strategy was studied and successfully used to identify target molecules from the depths of a developed TLC plate. By using this strategy, a hydrophobic sample of interest was enriched on the surface of the TLC plate in the presence of acetonitrile, in contrast to using water and methanol to identify hydrophilic samples. The successful enrichment of samples by specific solvents provided stable desorption/ionization efficiencies of compounds of interest and led to very good sensitivity near the attomole scale. The method was then used to monitor 4-dimethylaminopyridine (DMAP)-catalyzed acylation in preparation of bifunctional sulfonamides. The labile DMAP-acyl intermediate and final sulfonamide product were clearly identified on TLC plates without external purification or sample preparation. Furthermore, in combination with collision-induced dissociation (CID) to provide structural information, the technique was successfully used in the natural product discovery of anti-inflammatory flavonoids from Helminthostachys zeylanica, a traditional Chinese herb. The newly proposed method provides a very low background from silica supports or organic matrices in the low molecular weight range (100-1000 Da). The technique may greatly accelerate studies of metabolomics, drug discovery, and organic synthesis. PMID:23330148

  3. Comparative analysis of different plant oils by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Jakab, Annamaria; Héberger, Károly; Forgács, Esther

    2002-11-01

    Different vegetable oil samples (almond, avocado, corngerm, grapeseed, linseed, olive, peanut, pumpkin seed, soybean, sunflower, walnut, wheatgerm) were analyzed using high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry. A gradient elution technique was applied using acetone-acetonitrile eluent systems on an ODS column (Purospher, RP-18e, 125 x 4 mm, 5 microm). Identification of triacylglycerols (TAGs) was based on the pseudomolecular ion [M+1]+ and the diacylglycerol fragments. The positional isomers of triacylglycerol were identified from the relative intensities of the [M-RCO2]+ fragments. Linear discriminant analysis (LDA) as a common multivariate mathematical-statistical calculation was successfully used to distinguish the oils based on their TAG composition. LDA showed that 97.6% of the samples were classified correctly. PMID:12462617

  4. Positive and Negative Effects of Environmental Chemicals on Brain Function in Rodents

    Microsoft Academic Search

    Tomoko Tsuruoka; Tetsuya Fujimoto; Noboru Shiota; Makoto Monda; Yukiko Fueta; Toru Ishidao; Hajime Hori; Shuji Aou

    2010-01-01

    We investigated the effect of environmental chemicals on exploratory behavior and emotional behavior in Wistar rats, using\\u000a behavioral task such as open-field test, elevated plus maze test and forced swimming test. We used green odor and jasmine\\u000a tea odor as natural environmental chemicals and 1-bromopropane (1-BP) and bisphenol-A (BPA) as artificial environmental chemicals.\\u000a Green odor did not affect sensory-motor system

  5. Rapid characterization of chemical compounds in liquid and solid states using thermal desorption electrospray ionization mass spectrometry.

    PubMed

    Huang, Min-Zong; Zhou, Chi-Chang; Liu, De-Lin; Jhang, Siou-Sian; Cheng, Sy-Chyi; Shiea, Jentaie

    2013-10-01

    Rapid characterization of thermally stable chemical compounds in solid or liquid states is achieved through thermal desorption electrospray ionization mass spectrometry (TD-ESI/MS). A feature of this technique is that sampling, desorption, ionization, and mass spectrometric detection are four separate events with respect to time and location. A metal probe was used to sample analytes in their solid or liquid states. The probe was then inserted in a preheated oven to thermally desorb the analytes on the probe. The desorbed analytes were carried by a nitrogen gas stream into an ESI plume, where analyte ions were formed via interactions with charged solvent species generated in the ESI plume. The analyte ions were subsequently detected by a mass analyzer attached to the TD-ESI source. Quantification of acetaminophen in aqueous solutions using TD-ESI/MS was also performed in which a linear response for acetaminophen was obtained between 25 and 500 ppb (R(2) = 0.9978). The standard deviation for a reproducibility test for ten liquid samples was 9.6%. Since sample preparation for TD-ESI/MS is unnecessary, a typical analysis can be completed in less than 10 s. Analytes such as the active ingredients in over-the-counter drugs were rapidly characterized regardless of the different physical properties of said drugs, which included liquid eye drops, viscous cold syrup solution, ointment cream, and a drug tablet. This approach was also used to detect trace chemical compounds in illicit drugs and explosives, in which samples were obtained from the surfaces of a cell phone, piece of luggage made from hard plastic, business card, and wooden desk. PMID:24050317

  6. 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

  7. 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...

  8. Simultaneous detection of polar and nonpolar compounds by ambient mass spectrometry with a dual electrospray and atmospheric pressure chemical ionization source.

    PubMed

    Cheng, Sy-Chyi; Jhang, Siou-Sian; Huang, Min-Zong; Shiea, Jentaie

    2015-02-01

    A dual ionization source combining electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) was developed to simultaneously ionize both polar and nonpolar compounds. The source was constructed by inserting a fused silica capillary into a stainless steel column enclosed in a glass tube. A high dc voltage was applied to a methanol solution flowing in the fused silica capillary to generate an ESI plume at the capillary tip. A high ac voltage was applied to a ring electrode attached to the glass tube to generate plasma from the nitrogen gas flowing between the glass tube and the stainless steel column. The concentric arrangement of the ESI plume and the APCI plasma in the source ensured that analytes entering the ionization region interacted with both ESI and APCI primary ion species generated in the source. Because the high voltages required for ESI and APCI were independently applied and controlled, the dual ion source could be operated in ESI-only, APCI-only, or ESI+APCI modes. Analytes were introduced into the ESI and/or APCI plumes by irradiating sample surfaces with a continuous-wavelength laser or a pulsed laser beam. Analyte ions could also be produced by directing the dual ESI+APCI source toward sample surfaces for desorption and ionization. The ionization mechanisms involved in the dual ion source include Penning ionization, ion molecule reactions, and fused-droplet electrospray ionization. Standards of polycyclic aromatic hydrocarbons, angiotensin I, lidocaine, ferrocene, diesel, and rosemary oils were used for testing. Protonated analyte ions were detected in ESI-only mode, radical cations were detected in APCI-only mode, and both types of ions were detected in ESI+APCI mode. PMID:25562530

  9. EVALUATION OF DIPHENYLAMINE DERIVATIVES IN APPLE PEEL USING GRADIENT REVERSED-PHASE LIQUID CHROMATOGRAPHY WITH ULRAVIOLET-VISIBLE ABSORPTION AND ATMOSPHERIC PRESSURE CHEMICAL IONIZATION MASS SELECTIVE DETECTION.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A method was developed for extracting, identifying, and quantifying diphenylamine (DPA) derivatives in the peel of DPA-treated apples using gradient reversed-phase liquid chromatography with ultra-violet/visible absorption and atmospheric pressure chemical ionization detection (LC-UV/vis-APCIMS). C...

  10. 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 hydrocarbons (the primary components of gasoline) are difficult to analyze by mass spectrometry, because with the ability of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to analyze complex

  11. 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

  12. Electron dynamics upon ionization: Control of the timescale through chemical substitution and effect of nuclear motion.

    PubMed

    Vacher, Morgane; Mendive-Tapia, David; Bearpark, Michael J; Robb, Michael A

    2015-03-01

    Photoionization can generate a non-stationary electronic state, which leads to coupled electron-nuclear dynamics in molecules. In this article, we choose benzene cation as a prototype because vertical ionization of the neutral species leads to a Jahn-Teller degeneracy between ground and first excited states of the cation. Starting with equal populations of ground and first excited states, there is no electron dynamics in this case. However, if we add methyl substituents that break symmetry but do not radically alter the electronic structure, we see charge migration: oscillations in the spin density that we can correlate with particular localized electronic structures, with a period depending on the gap between the states initially populated. We have also investigated the effect of nuclear motion on electron dynamics using a complete active space self-consistent field (CASSCF) implementation of the Ehrenfest method, most previous theoretical studies of electron dynamics having been carried out with fixed nuclei. In toluene cation for instance, simulations where the nuclei are allowed to move show significant differences in the electron dynamics after 3 fs, compared to simulations with fixed nuclei. PMID:25747059

  13. Electron dynamics upon ionization: Control of the timescale through chemical substitution and effect of nuclear motion

    NASA Astrophysics Data System (ADS)

    Vacher, Morgane; Mendive-Tapia, David; Bearpark, Michael J.; Robb, Michael A.

    2015-03-01

    Photoionization can generate a non-stationary electronic state, which leads to coupled electron-nuclear dynamics in molecules. In this article, we choose benzene cation as a prototype because vertical ionization of the neutral species leads to a Jahn-Teller degeneracy between ground and first excited states of the cation. Starting with equal populations of ground and first excited states, there is no electron dynamics in this case. However, if we add methyl substituents that break symmetry but do not radically alter the electronic structure, we see charge migration: oscillations in the spin density that we can correlate with particular localized electronic structures, with a period depending on the gap between the states initially populated. We have also investigated the effect of nuclear motion on electron dynamics using a complete active space self-consistent field (CASSCF) implementation of the Ehrenfest method, most previous theoretical studies of electron dynamics having been carried out with fixed nuclei. In toluene cation for instance, simulations where the nuclei are allowed to move show significant differences in the electron dynamics after 3 fs, compared to simulations with fixed nuclei.

  14. Separation and identification of twelve catechins in tea using liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Zeeb, D J; Nelson, B C; Albert, K; Dalluge, J J

    2000-10-15

    A method has been developed for the direct microscale determination of 12 catechins in green and black tea infusions. The method is based on liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry (LC/APCI-MS). Standard catechin mixtures and tea infusions were analyzed by LC/APCI-MS with detection of protonated molecular ions and characteristic fragment ions for each compound. The identities of eight major catechins and caffeine in tea were established based on LC retention times and simultaneously recorded mass spectra. In addition, monitoring of the catechin-specific retro Diels-Alder fragment ion at m/z 139 throughout the chromatogram provided a unique fingerprint for catechin content in the samples that led to the identification of four minor chemically modified catechin derivatives in the infusions. This report is the first to describe the comprehensive determination of all 12 reported catechins in a single analysis. The utility of LC/APCI-MS for providing routine separation and identification of catechins at femtomole to low-picomole levels without extraction or sample pretreatment, and its potential as a standard analytical tool for the determination of polyphenols in natural products and biological fluids, are discussed. PMID:11055724

  15. Chemical chaperones reduce ionizing radiation-induced endoplasmic reticulum stress and cell death in IEC-6 cells.

    PubMed

    Lee, Eun Sang; Lee, Hae-June; Lee, Yoon-Jin; Jeong, Jae-Hoon; Kang, Seongman; Lim, Young-Bin

    2014-07-25

    Radiotherapy, which is one of the most effective approaches to the treatment of various cancers, plays an important role in malignant cell eradication in the pelvic area and abdomen. However, it also generates some degree of intestinal injury. Apoptosis in the intestinal epithelium is the primary pathological factor that initiates radiation-induced intestinal injury, but the mechanism by which ionizing radiation (IR) induces apoptosis in the intestinal epithelium is not clearly understood. Recently, IR has been shown to induce endoplasmic reticulum (ER) stress, thereby activating the unfolded protein response (UPR) signaling pathway in intestinal epithelial cells. However, the consequences of the IR-induced activation of the UPR signaling pathway on radiosensitivity in intestinal epithelial cells remain to be determined. In this study, we investigated the role of ER stress responses in IR-induced intestinal epithelial cell death. We show that chemical ER stress inducers, such as tunicamycin or thapsigargin, enhanced IR-induced caspase 3 activation and DNA fragmentation in intestinal epithelial cells. Knockdown of Xbp1 or Atf6 with small interfering RNA inhibited IR-induced caspase 3 activation. Treatment with chemical chaperones prevented ER stress and subsequent apoptosis in IR-exposed intestinal epithelial cells. Our results suggest a pro-apoptotic role of ER stress in IR-exposed intestinal epithelial cells. Furthermore, inhibiting ER stress may be an effective strategy to prevent IR-induced intestinal injury. PMID:24973711

  16. 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.

  17. 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

  18. Measurements of Nitrous Acid (HONO) Using Ion Drift - Chemical Ionization Mass Spectrometry during the 2009 SHARP Field Campaign

    NASA Astrophysics Data System (ADS)

    Levy, M. E.; Zhang, R.

    2013-12-01

    During the 2009 SHARP Field Campaign in Houston, TX, measurements of HONO were continuously conducted from May 1 to June 1 at a site located on the campus of the University of Houston. We have developed a novel approach for ambient measurements of nitrous acid (HONO) using ion drift - chemical ionization mass spectrometry (ID-CIMS). In our innovative method, HONO is ionized using the sulfur hexafluoride anion, representing the first application of this reagent ion under humid tropospheric conditions. In this presentation, we will discuss the temporal trends and sources of HONO, as well as, as the involvement of HONO in the formation of key atmospheric constituents, such as ozone. Diurnally, HONO concentration accumulates in the late afternoon, reaches a nighttime maximum, and declines rapidly after sunrise; the averaged daytime and nighttime concentrations are 0.15 × 0.05 and 0.26 × 0.04, respectively. The nighttime measured HONO peaks show strong correlations with the NO2 concentration, particle surface area, and soot mass concentration, indicating that the aerosol-phase chemistry represents a significant contributor to the HONO yield. A higher nighttime HONO peak concentration consistently precedes a higher and earlier ozone peak concentration of the following day, by about 20 ppb higher and four hours earlier than those with a lower preceding HONO peak concentration do. Using a kinetic approach, we estimate an uptake coefficient in the range of 6 x 10-4 to 2 x 10-3 for the heterogeneous conversion of NO2 to HONO on aerosol surfaces, which is necessary to account for the measured nighttime HONO peaks. Our results underscore the importance of aerosol heterogeneous chemistry in HONO production and the contributions of this non-photolytic HONO source to the radical budget and the photochemical ozone production in this region. Furthermore, because of its high detection sensitivity and fast-responding time, the ID-CIMS method described in this work may greatly facilitate HONO detection under typical tropospheric conditions.

  19. Evaluation of BDE-47 hydroxylation metabolic pathways based on a strong electron-withdrawing pentafluorobenzoyl derivatization gas chromatography/electron capture negative ionization quadrupole mass spectrometry.

    PubMed

    Zhai, Chao; Peng, Shunv; Yang, Limin; Wang, Qiuquan

    2014-07-15

    Understanding the metabolic pathways of polybrominated diphenyl ethers (PBDEs) is a key issue in the evaluation of their cytotoxicity after they enter the biota. In order to obtain more information concerning the metabolic pathways of PBDEs, we developed a strong electron-withdrawing pentafluorobenzoyl (PFBoyl) derivatization capillary gas chromatography/electron capture negative ionization quadrupole mass spectrometry (GC/ECNI-qMS). PFBoyl esterification greatly improves separation of the metabolites of PBDEs such as hydroxylated PBDEs (OH-PBDEs) and bromophenols (BPs) metabolites in rat liver microsomes (RLMs). On the other hand, the strong electron-withdrawing property of PFBoyl derivatized on OH-PBDEs and/or BPs makes cleavage of the ester bond on ECNI easier resulting in higher abundance of the structure-informative characteristic fragment ions at a high m/z region, which facilitate the identification of OH-PBDEs metabolites. Subsequent quantification can be performed by monitoring not only 79Br- (or 81Br-) but also their characteristic fragment ions, achieving more accurate isotope dilution quantification using GC/ECNI-qMS. These merits allow us to identify totally 12 metabolites of BDE-47, a typical example of PBDEs, in the RLMs in vitro incubation systems. In addition to the already known metabolites of BDE-47, one dihydroxylated 3,6-di-OH-BDE-47 and one dihydroxylated 3,5-di-OH-tetrabrominated dioxin were found. Moreover, the second hydroxylation took place on the same bromophenyl ring, where the first hydroxyl group was located, and was further confirmed via the identification of the dihydroxylated 2',6'-di-OH-BDE-28 of an asymmetric 2'-OH-BDE-28. This methodological development and its subsequent findings of the metabolic pathways of BDE-47 provided experimental evidence for understanding its dioxin-like behavior and endocrine disrupting risk. PMID:24925108

  20. A validated UPLC-MS/MS assay using negative ionization mode for high-throughput determination of pomalidomide in rat plasma.

    PubMed

    Iqbal, Muzaffar; Ezzeldin, Essam; Al-Rashood, Khalid A; Shakeel, Faiyaz

    2015-03-01

    In this study, a sensitive UPLC-MS/MS assay was developed and validated for high-throughput determination of pomalidomide in rat plasma using celecoxib as an internal standard (IS). Liquid liquid extraction using dichloromethane was employed to extract pomalidomide and IS from 200?L of plasma. Chromatographic separation was carried on Acquity BEH™ C18 column (50mm×2.1mm, 1.7?m) using an isocratic mobile phase of acetonitrile: 10mM ammonium acetate (80:20, v/v), at a flow rate of 0.250mL/min. Both pomalidomide and IS were eluted at 0.66±0.03 and 0.80±0.03min, respectively, with a total run time of 1.5min only. A triple quadruple tandem mass spectrometer using electrospray ionization in negative mode was employed for analyte detection. The precursor to product ion transitions of m/z 272.01?160.89 for pomalidomide and m/z 380.08?316.01 for IS were used to quantify them respectively, multiple reaction monitoring mode. The developed method was validated according to regulatory guideline for bioanalytical method validation. The linearity in plasma sample was achieved in the concentration range of 0.47-400ng/mL (r(2)?0.997). The intra and inter-day precision values were ?11.1% (RSD, %) whereas accuracy values ranged from -6.8 to 8.5% (RE, %). In addition, other validation results were within the acceptance criteria and the method was successfully applied in a pharmacokinetic study of pomalidomide in rats. PMID:25621435

  1. Identification of clinical coagulase-negative staphylococci, isolated in microbiology laboratories, by matrix-assisted laser desorption/ionization-time of flight mass spectrometry and two automated systems.

    PubMed

    Dupont, C; Sivadon-Tardy, V; Bille, E; Dauphin, B; Beretti, J L; Alvarez, A S; Degand, N; Ferroni, A; Rottman, M; Herrmann, J L; Nassif, X; Ronco, E; Carbonnelle, E

    2010-07-01

    A study was performed to compare matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS), linked to a recently engineered microbial identification database, and two rapid identification (ID) automated systems, BD Phoenix (Becton Dickinson Diagnostic Systems, France) and VITEK-2 (bioMérieux, Marcy L'Etoile, France), for the ID of coagulase-negative staphylococci (CoNS). Two hundred and thirty-four clinical isolates of CoNS representing 20 species were analyzed. All CoNS isolates were characterized by sodA gene sequencing, allowing interpretation of the ID results obtained using the respective database of each apparatus. Overall correct ID results were obtained in 93.2%, 75.6% and 75.2% of the cases with the MALDI-TOF-MS, Phoenix and VITEK-2 systems, respectively. Mis-ID and absence of results occurred in 1.7% and 5.1% of the cases with MALDI-TOF-MS, in 23.1% and 1.3% with the Phoenix, and in 13.7% and 0.9% with the VITEK-2 systems, respectively. In addition, with the latter automate, 10.3% of the IDs were proposed with remote possibility. When excluding the CoNS species not included in the databases of at least one of the three systems, the final percentage of correct results, Mis-ID and absence of ID were 97.4%, 1.3% and 1.3% with MALDI-TOF-MS, 79%, 21% and 0% with the Phoenix, and 78.6%, 10.3% and 0.9% with the VITEK-2 system, respectively. The present study demonstrates the robustness and high sensitivity of our microbial identification database used with MALDI-TOF-MS technology. This approach represents a powerful tool for the fast ID of clinical CoNS isolates. PMID:19732092

  2. 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

  3. A strategy for high-throughput analysis of levosimendan and its metabolites in human plasma samples using sequential negative and positive ionization liquid chromatography/tandem mass spectrometric detection.

    PubMed

    Zhang, Jun; Gage, Eric M; Ji, Qin C; El-Shourbagy, Tawakol A

    2007-01-01

    Levosimendan (Simdax) is an approved drug in approximately 40 countries and currently in phase III clinical studies in the USA and Europe. An accurate, high-throughput and rugged assay is critical to support these clinical trials. Due to the mechanism of drug metabolism, the drug and its active metabolites often have significant differences in their chemical properties. In order to achieve high assay throughput and low sample volumes, a single bioanalytical assay for the drug and its metabolites is preferred. However, this need may prevent the optimization of both high-performance liquid chromatography (HPLC) and mass spectrometric ionization conditions. The chemical properties of levosimendan are significantly different from those of its two active metabolites, OR-1855 and OR-1896. Here, we present a novel strategy for high-throughput analysis of levosimendan and its metabolites. A 96-well liquid/liquid extraction procedure was developed for sample preparation. A single liquid chromatography/tandem mass spectrometry (LC/MS/MS) system with two separate mobile phases, shared backwash solvent and conditioning solvent, was developed to perform sequential LC separation for levosimendan and the metabolites. Levosimendan was eluted by 5 mM ammonium acetate in 33.3% acetonitrile and detected using negative ionization mode MS/MS monitoring. The metabolites were eluted by 5 mM ammonium acetate and 0.2% acetic acid in 20% acetonitrile and detected with positive ionization mode MS/MS monitoring. The method has been demonstrated to have excellent precision and accuracy, with high assay ruggedness during method validation and clinical sample analysis. The linear dynamic ranges were approximately 200-50,000 pg/mL for levosimendan and approximately 500-130,000 pg/mL for both metabolites. The coefficient of determination (r2) for all analytes was greater than 0.9985. The intra-assay %CVs for QC samples were from 0.9% to 2.0% for levosimendan, 0.9% to 3.2% for OR-1855, and 0.4% to 4.9% for OR-1896. The inter-assay %CVs for QC samples were from 1.2% to 1.8% for levosimendan, 1.3% to 2.7% for OR-1855, and 1.4% to 3.4% for OR-1896. The mean % biases for QC samples were from 1.5% to 5.5% for levosimendan, -1.4% to 2.6% for OR-1855, and -0.3% to 4.5% for OR-1896. By using a single extraction approach coupled with sequential LC/MS/MS analysis for levosimendan and its metabolites, the assay maintained high throughput and low sample volume usage. PMID:17631672

  4. Rapid quantitation of plasma 2'-deoxyuridine by high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry and its application to pharmacodynamic studies in cancer patients.

    PubMed

    Li, Kong M; Rivory, Laurent P; Clarke, Stephen J

    2005-06-01

    A novel method employing high-performance liquid chromatograph-mass spectrometry (LC-MS) has been developed and validated for the quantitation of plasma 2'-deoxyuridine (UdR). It involves a plasma clean-up step with strong anion-exchange solid-phase extraction (SAX-SPE) followed by HPLC separation and atmospheric pressure chemical ionization mass spectrometry detection (APCI-MS) in a selected-ion monitoring (SIM) mode. The ionization conditions were optimised in negative ion mode to give the best intensity of the dominant formate adduct [M+HCOO]- at m/z 273. Retention times were 7.5 and 12.5 min for 2'-deoxyuridine and 5-iodo-2'-deoxyuridine, an iodinated analogue internal standard (IS), respectively. Peak area ratios of 2'-deoxyuridine to IS were used for regression analysis of the calibration curve. The latter was linear from 5 to 400 nmol/l using 1 ml sample volume of plasma. The average recovery was 81.5% and 78.6% for 2'-deoxyuridine and 5-iodo-deoxyuridine, respectively. The method provides sufficient sensitivity, precision, accuracy and selectivity for routine analysis of human plasma 2'-deoxyuridine concentration with the lowest limit of quantitation (LLOQ) of 5 nmol/l. Clinical studies in cancer patients treated with the new fluoropyrimidine analogue capecitabine (N4-pentoxycarbonyl-5'-5-fluorocytidine) have shown that plasma 2'-deoxyuridine was significantly elevated after 1 week of treatment, consistent with inhibition of thymidylate synthase (TS). These findings suggest that the mechanism of antiproliferative toxicity of capecitabine is at least partly due to TS inhibitory activity of its active metabolite 5-fluoro-2'-deoxyuridine monophosphate (FdUMP). Monitoring of plasma UdR concentrations have the potential to help clinicians to guide scheduling of capecitabine or other TS inhibitors in clinical trials. Marked differences of plasma 2'-deoxyuridine between human and rodents have also been confirmed. In conclusion, the LC-MS method developed is simple, highly selective and sensitive and permits pharmacodynamic studies of TS inhibitors in several species. PMID:15866500

  5. Negative Effects of Chemical Mutagenesis on the Adaptive Behavior of Vesicular Stomatitis Virus

    Microsoft Academic Search

    CAROLYN H. LEE; DOROTHY L. GILBERTSON; ISABEL S. NOVELLA; RAMON HUERTA; ESTEBAN DOMINGO; ANDJOHN J. HOLLAND

    1997-01-01

    Changes in adaptability of vesicular stomatitis virus (VSV) upon treatment with chemical mutagens have been investigated. Results showed no improvement in virus viability or adaptability at any given level of mutagenesis. In fact, increasing inhibition of virus production and adaptability was observed with increasing levels of mutagenesis. This was true for all tested VSV variants replicating either in changing or

  6. Airborne intercomparison of HOx measurements using laser-induced fluorescence and chemical ionization mass spectrometry during ARCTAS

    NASA Astrophysics Data System (ADS)

    Ren, X.; Mao, J.; Brune, W. H.; Cantrell, C. A.; Mauldin, R. L., III; Hornbrook, R. S.; Kosciuch, E.; Olson, J. R.; Crawford, J. H.; Chen, G.; Singh, H. B.

    2012-08-01

    The hydroxyl (OH) and hydroperoxyl (HO2) radicals, collectively called HOx, play central roles in tropospheric chemistry. Accurate measurements of OH and HO2 are critical to examine our understanding of atmospheric chemistry. Intercomparisons of different techniques for detecting OH and HO2 are vital to evaluate their measurement capabilities. Three instruments that measured OH and/or HO2 radicals were deployed on the NASA DC-8 aircraft throughout Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) in the spring and summer of 2008. One instrument was the Penn State Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) for OH and HO2 measurements based on Laser-Induced Fluorescence (LIF) spectroscopy. A second instrument was the NCAR Selected-Ion Chemical Ionization Mass Spectrometer (SI-CIMS) for OH measurement. A third instrument was the NCAR Peroxy Radical Chemical Ionization Mass Spectrometer (PeRCIMS) for HO2 measurement. Formal intercomparison of LIF and CIMS was conducted for the first time on a same aircraft platform. The three instruments were calibrated by quantitative photolysis of water vapor by ultraviolet (UV) light at 184.9 nm with three different calibration systems. The absolute accuracies were ±32% (2?) for the LIF instrument, ±65% (2?) for the SI-CIMS instrument, and ±50% (2?) for the PeRCIMS instrument. In general, good agreement was obtained between the CIMS and LIF measurements of both OH and HO2 measurements. Linear regression of the entire data set yields [OH]CIMS = 0.89 × [OH]LIF + 2.8 × 104 cm-3 with a correlation coefficient r2 = 0.72 for OH, and [HO2]CIMS = 0.86 × [HO2]LIF + 3.9 parts per trillion by volume (pptv, equivalent to pmol mol-1) with a correlation coefficient r2 = 0.72 for HO2. In general, the difference between CIMS and LIF instruments for OH and HO2 measurements can be explained by their combined measurement uncertainties. Comparison with box model results shows some similarities for both the CIMS and LIF measurements. First, the observed-to-modeled HO2 ratio increases greatly for higher NO mixing ratios, indicating that the model may not properly account for HOx sources that correlate with NO. Second, the observed-to-modeled OH ratio increases with increasing isoprene mixing ratios, suggesting either incomplete understanding of isoprene chemistry in the model or interferences in the measurements in environments where biogenic emissions dominate ambient volatile organic compounds.

  7. Airborne intercomparison of HOx measurements using laser-induced fluorescence and chemical ionization mass spectrometry during ARCTAS

    NASA Astrophysics Data System (ADS)

    Ren, X.; Mao, J.; Brune, W. H.; Cantrell, C. A.; Mauldin, R. L., III; Hornbrook, R. S.; Kosciuch, E.; Olson, J. R.; Crawford, J. H.; Chen, G.; Singh, H. B.

    2012-03-01

    The hydroxyl (OH) and hydroperoxyl (HO2) radicals, collectively called HOx, play central roles in tropospheric chemistry. Accurate measurements of OH and HO2 are critical to examine our understanding of atmospheric chemistry. Intercomparisons of different techniques for detecting OH and HO2 are vital to evaluate their measurement capabilities. Three instruments that measured OH and/or HO2 radicals were deployed on the NASA DC-8 aircraft throughout Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS), in the spring and summer of 2008. One instrument was the Penn State Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) for OH and HO2 measurements based on Laser-Induced Fluorescence (LIF) spectroscopy. A second instrument was the NCAR Selected-Ion Chemical Ionization Mass Spectrometer (SI-CIMS) for OH measurement. A third instrument was the NCAR Peroxy Radical Chemical Ionization Mass Spectrometer (PeRCIMS) for HO2 measurement. Formal intercomparison of LIF and CIMS was conducted for the first time on a same aircraft platform. The three instruments were calibrated by quantitative photolysis of water vapor by UV light at 184.9 nm with three different calibration systems. The absolute accuracies were ±32% (2?) for the LIF instrument, ±65% (2?) for the SI-CIMS instrument, and ±50% (2?) for the PeRCIMS instrument. In general, good agreement was obtained between the CIMS and LIF measurements of both OH and HO2 measurements. Linear regression of the entire data set yields [OH]CIMS = 0.89 × [OH]LIF + 2.8 × 105 cm-3 with a correlation coefficient, r2 = 0.72 for OH and [HO2]CIMS = 0.86 × [HO2]LIF + 3.9 parts per trillion by volume (pptv, equivalent to pmol mol-1) with a correlation coefficient, r2 = 0.72 for HO2. In general, the difference between CIMS and LIF instruments for OH and HO2 measurements can be explained by their combined measurement uncertainties. Comparison with box model results shows some similarities for both the CIMS and LIF measurements. First, the observed-to-modeled HO2 ratio increases greatly for higher NO mixing ratios, indicating that the model may not properly account for HOx sources that correlate with NO. Second, the observed-to-modeled OH ratio increases with increasing isoprene mixing ratios, suggesting either incomplete understanding of isoprene chemistry in the model or interferences in the measurements in environments where biogenic emissions dominate ambient volatile organic compounds.

  8. 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.

  9. Eddy Correlation Measurements of the Air/Sea Flux of DMS Using Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Marandino, C. A.; Debruyn, W. J.; Saltzman, E. S.

    2003-12-01

    The physical and chemical processes controlling gas exchange across the air/sea interface are not well understood. Many laboratory and field studies of the physical controls on gas exchange have been performed using indirect mass balance measurement techniques, but there have been few direct gas flux measurements over the ocean. Eddy correlation is a micrometeorological technique, which can measure fluxes directly. The use of this technique for trace gas flux measurements has been limited in part due to the lack of sufficiently sensitive, fast-response gas detectors. Atmospheric pressure chemical ionization mass spectrometry (API/CIMS) is a highly sensitive, fast response detection method. We carried out a field study at the Scripps Institute of Oceanography pier to test the use of API/CIMS for eddy correlation flux measurements of dimethylsulfide (DMS). Cospectra of vertical winds and DMS demonstrate that flux from the sea surface was routinely detected. The API/CIMS detected atmospheric fluctuations less than 0.5 Hz. This frequency cut-off probably reflects attenuation in the inlet tubing rather than in the detector itself. The partial pressure of DMS in surface seawater was also determined using the API/CIMS, after equilibration with N2 in a continuous flow membrane equilibrator. Gas exchange coefficients were computed from the flux and air/sea concentration gradient. Gas transfer coefficients determined in this study ranged from 0.66 cm/hr to 38.43 cm/hr, for mean horizontal wind speeds ranging from 1 to 6 m/s. The gas transfer coefficients are positively correlated with wind speed, but are significantly greater than current estimates of gas transfer coefficients at similar wind speeds over the ocean. These elevated gas transfer coefficients probably reflect enhanced water-side turbulence induced by the interaction of wave motion with the shallow bottom at this site.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  11. 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

  12. 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.

  13. Analyses of polycyclic aromatic hydrocarbons in seafood by capillary electrochromatography-atmospheric pressure chemical ionization/mass spectrometry.

    PubMed

    Cheng, Yi-Jie; Huang, Sing-Hao; Chiu, Ju-Yin; Liu, Wan-Ling; Huang, Hsi-Ya

    2013-10-25

    In this work, an on-line preconcentration capillary electrochromatographic (CEC) separation coupled with atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) was used for 16 PAHs analyses, in which poly(stearyl methacrylate-divinylbenzene) (poly(SMA-DVB)) monolith was used as the separation column. With variations in the effective length of poly(SMA-DVB) monolith as well as the volume fraction of acetonitrile (ACN) in the mobile phase, both separation and resolution were improved. A poly(SMA-DVB) monolith of 50-cm effective length (i.e. 50-cm column length filled with polymer) and a two-step step-gradient elution (by changing the ACN levels of the mobile phase starting with an initial of 70% up to 80% with 30-min time interval), which provided baseline separation for PAHs solutes (except for chrysene and benzo[a]anthracene) within 50 min, were employed as the optimal chromatographic conditions. In contrast to the other mass spectrometer parameters (nebulizer gas pressure, vaporizer temperature, corona current) as well as on-line preconcentration parameter (the ACN level in the sample matrix), the sheath liquid composition (methanol/water in the ratio of 3:1) and the sample injection time (40 min) were found as the predominant factors that control the sensitivity of PAHs determination. Finally, this on-line preconcentration CEC-APCI-MS method determined PAH residues in seafood samples successfully with as low as 10 ng/g level. PMID:23992841

  14. Analysis of polycyclic aromatic hydrocarbons using desorption atmospheric pressure chemical ionization coupled to a portable mass spectrometer.

    PubMed

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

    2015-02-01

    Desorption atmospheric pressure chemical ionization (DAPCI) is implemented on a portable mass spectrometer and applied to the direct detection of polycyclic aromatic hydrocarbons (PAHs) and alkyl substituted benzenes. The presence of these compounds in the environment poses a significant threat to the health of both humans and wildlife because of their carcinogenic, toxic, and mutagenic properties. As such, instant detection outside of the laboratory is of particular importance to allow in-situ measurement at the source. Using a rapid, high throughput, miniature, handheld mass spectrometer, several alkyl substituted benzenes and PAHs (i.e., 1,2,3,5-tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, fluoranthene, anthracene, benzo[k]fluoranthene, dibenz[a,h]anthracene, acenaphthene, indeno[1,2,3-c,d]pyrene, 9-ethylfluorene, and 1-benzyl-3-methyl-naphthalene) were identified and characterized using tandem mass spectrometry (MS/MS) from ambient surfaces, in the open air. This method can provide almost instantaneous information while minimizing sample preparation, which is advantageous in terms of both cost and simplicity of analysis. This MS-based technique is applicable to a wide range of environmental organic molecules. PMID:25503470

  15. Triacylglycerol Analysis of Potential Margarine Base Stocks by High-Performance Liquid Chromatography with Atmospheric Pressure Chemical Ionization Mass Spectrometry and Flame Ionization Detection

    Microsoft Academic Search

    W. Craig Byrdwell; William E. Neff; Gary R. List

    2001-01-01

    Several margarine base stock candidates have previously been prepared for the purpose of finding better, more oxidatively stable food components: high-saturate vegetable oils, randomized vegetable oils, vegetable oil-hard stock blends, and interesterified vegetable oil-hard stock blends. Here are reported the triacylglycerol compositions of these products, determined using reverse-phase high- performance liquid chromatography (HPLC) coupled with a flame ionization detector or

  16. Study on glow discharge effects on catalyst films for growing aligned carbon nanofibers in negative bias-enhanced hot filament chemical vapor deposition system

    Microsoft Academic Search

    B. B. Wang; Soonil Lee; H. Yan; B. H. Hou; Seungho Choi

    2005-01-01

    Aligned carbon nanofibers (ACNFs) were grown on silicon substrates coated with NiFe catalyst films by negative bias-enhanced hot filament chemical vapor deposition (CVD). The growth and structure of the aligned carbon nanofibers were investigated by scanning electron microscopy (SEM). The results indicate that the aligned carbon nanofibers could be synthesized after the glow discharge appears when the negative bias is

  17. Rapid discovery and global characterization of chemical constituents and rats metabolites of Phellodendri amurensis cortex by ultra-performance liquid chromatography-electrospray ionization/quadrupole-time-of-flight mass spectrometry coupled with pattern recognition approach.

    PubMed

    Wang, Huiyu; Yan, Guangli; Zhang, Aihua; Li, Yuan; Wang, Yangyang; Sun, Hui; Wu, Xiuhong; Wang, Xijun

    2013-06-01

    To discover and screen the constituents or metabolites absorbed into blood after oral administration of herbal medicines tends to be more and more difficult. In this work, an integrative pattern recognition approach of principal component analysis (PCA) and orthogonal partial least squared discriminant analysis (OPLS-DA) was successfully applied for rapid discovery of natural compounds from herbal medicines. A rapid, sensitive, and reliable ultra performance liquid chromatography coupled with electrospray ionization/quadrupole-time-of-flight mass spectrometry (UPLC-ESI-Q-TOF-MS) method with Masslynx™ software was established to characterize the chemical constituents and rats metabolites of Phellodendri amurensis cortex (Guan Huangbai, GHB). The analysis was performed on a Waters UPLC HSS T3 column (2.1 × 100 mm, 1.8 ?m) using gradient elution system. A hyphenated electrospray ionization and quadrupole-time-of-flight analyzer was used for the determination of accurate mass of the protonated or deprotonated molecule and fragment ion in both negative and positive modes. A total of 46 peaks were obtained, 41 of which were tentatively characterized from GHB. In the S-plot of OPLS-DA, 24 interested ions (17 ions in positive mode and 6 ions in negative mode) were extracted, among them, 12 absorbed prototype components of GHB and 12 metabolites were identified in vivo. Major metabolic reactions of GHB were demethylation, methylation and glucuronidation. This is the first report on systematic analysis of chemical constituents and in vivo metabolites of GHB. It is concluded that UPLC-MS coupled with pattern recognition approach for the identification of herbal constituents in biological samples has been successfully developed. The method can also be applied to rapid discovery and global characterization of the constituents in rat serum after oral administration of other herbal medicines. PMID:23608925

  18. Chemical kinetics of low pressure high density hydrogen plasmas: application to negative ion sources for ITER

    NASA Astrophysics Data System (ADS)

    Gaboriau, F.; Boeuf, J. P.

    2014-12-01

    This paper presents a systematic kinetic characterization of a low pressure high power hydrogen plasma. The plasma physics is described with a global model coupled to a homogeneous kinetic model for hydrogen. This model involves reactions which describe the vibrational and electronic excited kinetics of H2, the positive ?ft( H{+}{,}H2{+}{,}H3{+} \\right) and negative (H?) ion kinetics and the H chemistry. This enables the estimation of the particle density and the electron temperature and their evolutions as a function of power (1–100 kW) and pressure (0.3–4 Pa). These very specific plasma conditions involve physical phenomena not occurring in more usual plasmas, such as gas depletion. To account for this gas depletion, we incorporate in the global model both the H neutral heat equation to calculate the H temperature, and the gas pumping. Indeed, the gas depletion is mainly due to H atom heating leading to a higher pumping loss for H atoms. The consideration of the gas depletion allows us to obtain similar behaviors to the experiments when varying power and pressure. From an accurate analysis of the main formation and destruction pathways for each particle, the species kinetics is discussed and a simplified kinetic model that may be used to describe the non-equilibrium plasma in the negative source for ITER is proposed. Finally, the results point to strong coupling existing between the H atom wall recombination coefficient ?H and the gas depletion. An increase of ?H reduces the gas depletion, affecting the electron temperature and the electron density as well as the whole plasma kinetics.

  19. CHEMICAL ANALYSIS OF A DIFFUSE CLOUD ALONG A LINE OF SIGHT TOWARD W51: MOLECULAR FRACTION AND COSMIC-RAY IONIZATION RATE

    SciTech Connect

    Indriolo, Nick; Neufeld, D. A. [Department of Physics and Astronomy, Johns Hopkins University, Baltimore, MD 21218 (United States); Gerin, M. [LERMA, CNRS, Observatoire de Paris and ENS, F-75231 Paris Cedex 05 (France); Geballe, T. R. [Gemini Observatory, Hilo, HI 96720 (United States); Black, J. H. [Department of Earth and Space Sciences, Chalmers University of Technology, Onsala Space Observatory, SE-43992 Onsala (Sweden); Menten, K. M. [MPI fuer Radioastronomie, D-53121 Bonn (Germany); Goicoechea, J. R. [Departamento de Astrofisica, Centro de Astrobiologia (CSIC-INTA), E-28850 Madrid (Spain)

    2012-10-20

    Absorption lines from the molecules OH{sup +}, H{sub 2}O{sup +}, and H{sup +} {sub 3} have been observed in a diffuse molecular cloud along a line of sight near W51 IRS2. We present the first chemical analysis that combines the information provided by all three of these species. Together, OH{sup +} and H{sub 2}O{sup +} are used to determine the molecular hydrogen fraction in the outskirts of the observed cloud, as well as the cosmic-ray ionization rate of atomic hydrogen. H{sup +} {sub 3} is used to infer the cosmic-ray ionization rate of H{sub 2} in the molecular interior of the cloud, which we find to be {zeta}{sub 2} = (4.8 {+-} 3.4) Multiplication-Sign 10{sup -16} s{sup -1}. Combining the results from all three species we find an efficiency factor-defined as the ratio of the formation rate of OH{sup +} to the cosmic-ray ionization rate of H-of {epsilon} = 0.07 {+-} 0.04, much lower than predicted by chemical models. This is an important step in the future use of OH{sup +} and H{sub 2}O{sup +} on their own as tracers of the cosmic-ray ionization rate.

  20. Regioisomeric analysis of triacylglycerols using silver-ion liquid chromatography–atmospheric pressure chemical ionization mass spectrometry: Comparison of five different mass analyzers

    Microsoft Academic Search

    Michal Hol?apek; Hana Dvo?áková; Miroslav Lísa; Ana Jimenéz Girón; Pat Sandra; Josef Cva?ka

    2010-01-01

    Silver-ion high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionization mass spectrometry (APCI-MS) is used for the regioisomeric analysis of triacylglycerols (TGs). Standard mixtures of TG regioisomers are prepared by the randomization reaction from 8 mono-acid TG standards (tripalmitin, tristearin, triarachidin, triolein, trielaidin, trilinolein, trilinolenin and tri-gamma-linolenin). In total, 32 different regioisomeric doublets and 11 triplets are synthesized, separated

  1. Analysis of aristolochic acid in nine sources of Xixin, a traditional Chinese medicine, by liquid chromatography\\/atmospheric pressure chemical ionization\\/tandem mass spectrometry

    Microsoft Academic Search

    Ting-Ting Jong; Maw-Rong Lee; Shun-Sheng Hsiao; Jar-Lung Hsai; Tian-Shung Wu; Shu Tuan Chiang; Shao-Qing Cai

    2003-01-01

    Aristolochic acid I (AA-I), which is a known nephrotoxin, is found in a commonly used Chinese medicine, Xixin, that originates from nine Asarum species (Aristolochiaceae) found in China. A method has been developed using reversed-phase liquid chromatography coupled with atmospheric pressure chemical ionization (APCI) tandem mass spectrometry under the positive ion detection mode [LC\\/(+)APCI\\/MS\\/MS] to determine the amount of AA-I

  2. Characterization of triacylglycerol and diacylglycerol composition of plant oils using high-performance liquid chromatography–atmospheric pressure chemical ionization mass spectrometry

    Microsoft Academic Search

    Michal Hol?apek; Pavel Jandera; Petr Zderadi?ka; Lucie Hrubá

    2003-01-01

    Triacylglycerols (TGs) and diacylglycerols (DGs) in 16 plant oil samples (hazelnut, pistachio, poppy-seed, almond, palm, Brazil-nut, rapeseed, macadamia, soyabean, sunflower, linseed, Dracocephalum moldavica, evening primrose, corn, amaranth, Silybum arianum) were analyzed by HPLC–MS with atmospheric pressure chemical ionization (APCI) and UV detection at 205 nm on two Nova-Pak C18 chromatographic columns connected in series. A single chromatographic column and non-aqueous

  3. 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

  4. Determination of melamine and cyanuric acid in powdered milk using injection-port derivatization and gas chromatography–tandem mass spectrometry with furan chemical ionization

    Microsoft Academic Search

    Shin-Hwa Tzing; Wang-Hsien Ding

    2010-01-01

    A reliable, sensitive and eco-friendly injection-port trimethylsilylated (TMS) derivatization and gas chromatography–tandem mass spectrometry (GC–MS\\/MS) with furan chemical ionization (furan-CI) method was developed to determine melamine and cyanuric acid in powdered milk samples. The effects of several parameters related to the TMS-derivatization process (i.e., injection-port temperature, residence time and volume of silylating agent) and of various CI agents were investigated.

  5. 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

  6. Identification of nonprotein amino acids from cycad seeds as N-ethoxycarbonyl ethyl ester derivatives by positive chemical-ionization gas chromatography-mass spectrometry

    Microsoft Academic Search

    Meide Pan; Tom J. Mabry; Ping Cao; Mehdi Moini

    1997-01-01

    Nonprotein amino acids from nine species of cycad seeds were analyzed as N-ethoxycarbonyl ethyl ester (ECEE) derivatives by positive chemical-ionization gas chromatography-mass spectrometry. Based on the retention times and mass spectrometry analyses, 12 nonprotein amino acids were identified in these seeds. In addition to the excitatory and putative neurotoxin ß-N-methylamino-l-alanine (BMAA), the known neurotoxin ß-N-oxalylamino-l-alanine (BOAA) was detected from the

  7. Array of Chemically Etched Fused Silica Emitters for Improving the Sensitivity and Quantitation of Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Kelly, Ryan T.; Page, Jason S.; Tang, Keqi; Smith, Richard D.

    2007-06-01

    An array of emitters has been developed for increasing the sensitivity of electrospray ionization mass spectrometry (ESI-MS). The linear array consists of 19 chemically etched fused silica capillaries arranged with 500 µm (center-to-center) spacing. The multi-emitter device has a low dead volume to facilitate coupling to capillary liquid chromatography (LC) separations. The high aspect ratio of the emitters enables operation at flow rates as low as 20 nL/min/emitter, effectively extending the benefits of nanoelectrospray to higher flow rate analyses. To accommodate the larger ion current produced by the emitter array, a multi-capillary inlet to the mass spectrometer was also constructed. The inlet, which matched the dimensions of the emitter array, effectively preserved ion transmission efficiency. Standard reserpine solutions of varying concentration were electrosprayed at 1 µL/min using the multi-emitter/multi-inlet combination, and compared to a standard, single emitter configuration. A nine-fold sensitivity enhancement was observed for the multi-emitter relative to the single emitter. A bovine serum albumin tryptic digest was also analyzed and resulted in a sensitivity increase ranging from 2.4 to 12.3-fold for the detected tryptic peptides; the varying response was attributed to reduced ion suppression under the nano-ESI conditions afforded by the emitter array. An equimolar mixture of leucine enkephalin and maltopentaose was studied to verify that ion suppression is indeed reduced for the multi-ESI array relative to a single emitter over a range of flow rates.

  8. Application of FIGAERO (Filter Inlet for Gases and AEROsol) coupled to a high resolution time of flight chemical ionization mass spectrometer to field and chamber organic aerosol: Implications for carboxylic acid formation and gas-particle partitioning from monoterpene oxidation

    NASA Astrophysics Data System (ADS)

    Lopez-Hilfiker, F.; Mohr, C.; Ehn, M.; Rubach, F.; Mentel, T. F.; Kleist, E.; Wildt, J.; Thornton, J. A.

    2013-12-01

    We present measurements of a large suite of gas and particle phase carboxylic acid containing compounds made with a Filter Inlet for Gas and AEROsol (FIGAERO) coupled to a high resolution time of flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. A prototype operated with acetate negative ion proton transfer chemistry was deployed on the Julich Plant Atmosphere Chamber to study a-pinene oxidation, and a modified version was deployed at the SMEAR II forest station in Hyytiälä, Finland and SOAS, in Brent Alabama. We focus here on results from JPAC and Hyytiälä, where we utilized the same ionization method most selective towards carboxylic acids. In all locations, 100's of organic acid compounds were observed in the gas and particles and many of the same composition acids detected in the gas-phase were detected in the particles upon temperature programmed thermal desorption. Particulate organics detected by FIGAERO are highly correlated with organic aerosol mass measured by an AMS, providing additional volatility and molecular level information about collected aerosol. The fraction of a given compound measured in the particle phase follows expected trends with elemental composition, but many compounds would not be well described by an absorptive partitioning model assuming unity activity coefficients. Moreover the detailed structure in the thermal desorption signals reveals a contribution from thermal decomposition of large molecular weight organics and or oligomers with implications for partitioning measurements and model validation

  9. Observation of negative differential resistance and electrical bi-stability in chemically synthesized ZnO nanorods

    NASA Astrophysics Data System (ADS)

    Roy, Nandini; Chowdhury, Avijit; Roy, Asim

    2014-06-01

    Zinc oxide nanorods/p-Si heterostructures have been fabricated by depositing the chemically synthesized ZnO nanorods on p-type silicon substrate. Heterostructure shows electrical bi-stability and negative differential resistance (NDR) only at the beginning of the forward bias region, and these phenomena have been explained with the help of energy band diagram. An explanation is proposed for the origin of electrical bi-stability in light of the electric field induced charge transfer across the junction, and the NDR phenomena could be attributed to interfacial traps and defect level that arises due to oxygen and zinc interstitial vacancies. Room temperature photoluminescence measurement of ZnO nanorods exhibits the emission peaks at about 466 nm and 566 nm which are attributed to oxygen vacancies and Zn interstitials. A correlation between NDR and blue emission phenomena in the ZnO nanorods due to defects states has been established.

  10. Principles of Electrospray Ionization

    PubMed Central

    Wilm, Matthias

    2011-01-01

    Electrospray ionization is today the most widely used ionization technique in chemical and biochemical analysis. Interfaced with a mass spectrometer it allows the investigation of the molecular composition of liquid samples. With electrospray a large variety of chemical substances can be ionized. There is no limitation in mass which thus enables even the investigation of large noncovalent protein complexes. Its high ionization efficiency profoundly changed biomolecular sciences because proteins can be identified and quantified on trace amounts in a high throughput fashion. This review article focuses mainly on the exploration of the underlying ionization mechanism. Some ionization characteristics are discussed that are related to this mechanism. Typical spectra of peptides, proteins, and noncovalent complexes are shown and the quantitative character of spectra is highlighted. Finally the possibilities and limitations in measuring the association constant of bivalent noncovalent complexes are described. PMID:21742801

  11. Are clusters important in understanding the mechanisms in atmospheric pressure ionization? Part 1: Reagent ion generation and chemical control of ion populations.

    PubMed

    Klee, Sonja; Derpmann, Valerie; Wißdorf, Walter; Klopotowski, Sebastian; Kersten, Hendrik; Brockmann, Klaus J; Benter, Thorsten; Albrecht, Sascha; Bruins, Andries P; Dousty, Faezeh; Kauppila, Tiina J; Kostiainen, Risto; O'Brien, Rob; Robb, Damon B; Syage, Jack A

    2014-08-01

    It is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region. PMID:24850441

  12. Electrospray ionization\\/mass spectrometry compatible reversed-phase separation of phospholipids: piperidine as a post column modifier for negative ion detection

    Microsoft Academic Search

    Cory A Lytle; Ying Dong Gan; David C White

    2000-01-01

    An electrospray ionization (ESI) compatible separation of phospholipids (PL), phosphatidylglycerol (PG), phosphatidylethanolamine (PE), and phosphatidylcholine (PC), was performed on a C18 column by reversed phase High Performance Liquid Chromatography (HPLC) with minimal ESI suppression. The mobile phase, used isocratically, consisted of methanol and water. ESI was used to efficiently transfer the ions present in solution to the gas phase for

  13. Analysis of organic aerosols using a micro-orifice volatilization impactor coupled to an atmospheric-pressure chemical ionization mass spectrometer.

    PubMed

    Brüggemann, Martin; Vogel, Alexander Lucas; Hoffmann, Thorsten

    2014-01-01

    We present the development and characterization of a combination of a micro-orifice volatilization impactor (MOVI) and an ion trap mass spectrometer (IT/MS) with an atmospheric-pressure chemical ionization (APCI) source. The MOVI is a multi-jet impactor with 100 nozzles, allowing the collection of aerosol particles by inertial impaction on a deposition plate. The pressure drop behind the nozzles is approximately 5%, resulting in a pressure of 96kPa on the collection surface for ambient pressures of 101.3 kPa. The cut-point diameter (diameter of 50% collection efficiency) is at 0.13 microm for a sampling flow rate of 10 L min(-1). After the collection step, aerosol particles are evaporated by heating the impaction surface and transferred into the APCI-IT/MS for detection of the analytes. APCI was used in the negative ion mode to detect predominantly mono- and dicarboxylic acids, which are major oxidation products of biogenic terpenes. The MOVI-APCI-IT/MS instrument was used for the analysis of laboratory-generated secondary organic aerosol (SOA), which was generated by ozonolysis of alpha-pinene in a 100 L continuous-flow reactor under dark and dry conditions. The combination of the MOVI with an APCI-IT/MS improved the detection Limits for small dicarboxylic acids, such as pinic acid, compared to online measurements by APCI-IT/MS. The Limits of detection and quantification for pinic acid were determined by external calibration to 4.4 ng and 13.2 ng, respectively. During a field campaign in the southern Rocky Mountains (USA) in summer 2011 (BEACHON-RoMBAS), the MOVI-APCI-IT/MS was applied for the analysis of ambient organic aerosols and the quantification of individual biogenic SOA marker compounds. Based on a measurement frequency of approximately 5 h, a diurnal cycle for pinic acid in the sampled aerosol particles was found with maximum concentrations at night (median: 10.1 ngm(-3)) and minimum concentrations during the day (median: 8.2 ng m(-3)), which is likely due to the partitioning behavior of pinic acid and the changing phase state of the organic aerosol particles with changing relative humidity. PMID:24881453

  14. 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.

  15. Analysis of estrogens in river water and effluents using solid-phase extraction and gas chromatography–negative chemical ionisation mass spectrometry of the pentafluorobenzoyl derivatives

    Microsoft Academic Search

    Xiao-Yao Xiao; David V McCalley; James McEvoy

    2001-01-01

    A procedure was developed for the analysis of estrogens in environmental water and effluents. Samples were extracted by passing through polymer-impregnated solid-phase extraction discs or C18 cartridges, followed by gas chromatography–negative chemical ionisation mass spectrometry of the pentafluorobenzoyl derivatives. The derivatives were stable and gave diagnostic negative molecular ions as the base peak for each of the major estrogens studied.

  16. Rare earth oxide catalyzed oxidation of rhenium to ReOâ⁻ and ReOâ⁻ as observed by negative surface ionization mass spectrometry

    Microsoft Academic Search

    Delmore

    1987-01-01

    A surface ionization mass spectrometer was used to observe the in situ formation of ReOâ⁻ and ReOâ⁻ gas-phase ions resulting from the rare earth oxide catalyzed reaction of water with metallic rhenium. Water was found to be 6-10-fold more efficient than oxygen as an oxidizer at temperatures around 1100°C. Normal, oxygen-18 enriched, and deuteriated water were used to elucidate the

  17. Interlaboratory study comparison of the 15-day intact adult male rat screening assay: evaluation of an antithyroid chemical and a negative control chemical.

    PubMed

    Becker, Richard A; Bergfelt, Don R; Borghoff, Susan; Davis, Jeffrey P; Hamby, Bonnie T; O'Connor, John C; Kaplan, A Michael; Sloan, Carol S; Tyl, Rochelle W; Wade, Michael; Marty, Mary Sue

    2012-02-01

    Validation of the 15-day intact adult male rat screening assay (IAMRSA), an endocrine activity screen, was extended beyond the 28 substances evaluated to date. Two independent laboratories evaluated specificity using allyl alcohol (AA), a putative negative control, and DE-71 (technical grade pentabromodiphenyl ether) for comparison with previous pubertal assays that demonstrated thyroid effects. Male rats (15/group) were gavaged daily with AA (0, 10, 30, or 40 mg/kg/day) or DE-71 (0, 3, 30, or 60 mg/kg/day) for 15 days. Body and organ weights and serum hormone concentrations were measured, and a limited histopathological assessment was conducted. AA results were considered negative at doses that did not exceed the maximum tolerated dose (MTD); effects reported were dose-related decreases in weight gain, increased liver weights and, although the pattern varied across studies, alterations in some androgen-sensitive endpoints in the high-dose where the maximum tolerated dose was exceeded. In the DE-71 studies, dose-dependent increases in liver weights (consistent with hepatic enzyme induction), decreases in tri-iodothyronine and thyroxine, concomitant thyroid stimulating hormone increases were observed and one laboratory reported histopathological thyroid changes in mid- and high-dose groups, and the other increased thyroid weights. For DE-71, the IAMRSA was comparable in sensitivity to the pubertal assays. Overall, the specificity and sensitivity of the IAMRSA for deployment in an endocrine screening battery are supported. However, differentiating primary endocrine-mediated effects from secondary effects caused by systemic toxicity will be challenging, emphasizing the need to utilize a battery of assays and a weight of evidence approach when evaluating the potential endocrine activity of chemicals. PMID:22127959

  18. A Micro-Orifice Volatilization Impactor coupled to a Chemical Ionization Mass Spectrometer for the detection of organic acids in atmospheric aerosol particles

    NASA Astrophysics Data System (ADS)

    Yatavelli, R. L.; Thornton, J. A.

    2007-12-01

    Significant uncertainties related to sources and removal processes of particulate organic matter persist due, in part, to a poor understanding of the molecular-level composition. To address these issues, we are developing a novel technique that couples a micro-orifice volatilization impactor (MOVI) to a chemical ionization mass spectrometer (CIMS) for fast, in situ measurements of specific organic acids expected to be in atmospheric particles. The MOVI-CIMS process has three steps: 1) aerosol collection by inertial impaction, 2) volatilization and sample transfer, and 3) chemical ionization and detection using a quadrupole mass spectrometer. We present results from laboratory characterization of two MOVI designs, one operating at low pressure (60 Torr) and the other at near ambient pressure. The low-pressure impactor has a theoretical cut point of 40nm while the atmospheric pressure impactor (API) has a theoretical cut point of 280nm with a pressure drop of less than 5%. We compare the advantages and disadvantages of these two designs in terms of typical atmospheric particle size distributions. Experimental tests of their theoretical cut-points are used to assess the importance of jet-to- plate distance and particle bounce. In addition, we demonstrate the utility of the MOVI-CIMS technique by employing it in studies of heterogeneous oxidation of particle organics and of secondary organic aerosol formation from biogenic hydrocarbon oxidation. Based on typical signal-to-noise ratio, the MOVI-CIMS demonstrates a detection limit of ~50 ng for monocarboxylic acids when using the LPI version and the iodide ion as a chemical ionization reagent. Preliminary results suggest even lower detection limits are possible with other reagent ions.

  19. Metal-organic chemical vapor-deposited cobalt oxide films as negative electrodes for thin film Li-ion battery

    NASA Astrophysics Data System (ADS)

    Jena, Anirudha; Munichandraiah, N.; Shivashankar, S. A.

    2015-03-01

    In this study, thin films of cobalt oxide (Co3O4) have been grown by the metal-organic chemical vapor deposition (MOCVD) technique on stainless steel substrate at two preferred temperatures (450 °C and 500 °C), using cobalt acetylacetonate dihydrate as precursor. Spherical as well as columnar microstructures of Co3O4 have been observed under controlled growth conditions. Further investigations reveal these films are phase-pure, well crystallized and carbon-free. High-resolution TEM analysis confirms that each columnar structure is a continuous stack of minute crystals. Comparative study between these Co3O4 films grown at 450 °C and 500 °C has been carried out for their application as negative electrodes in Li-ion batteries. Our method of electrode fabrication leads to a coating of active material directly on current collector without any use of external additives. A high specific capacity of 1168 micro Ah cm-2 ?m-1 has been measured reproducibly for the film deposited at 500°C with columnar morphology. Further, high rate capability is observed when cycled at different current densities. The Co3O4 electrode with columnar structure has a specific capacity 38% higher than the electrode with spherical microstructure (grown at 450°C). Impedance measurements on the Co3O4 electrode grown at 500 °C also carried out to study the kinetics of the electrode process.

  20. 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

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

    E-print Network

    world's first C60 SIMS FT-ICR MS. Unique capabilities for imaging biological samples: High mass accuracy (ppm) High mass resolving power (m/m50% >3,000,000) Tandem MS capabilities Developed nanosprayDevelopment of New Soft Ionization Mass Spectrometry Approaches for Spatial Imaging of Complex

  2. 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.

  3. Identification of volatile and semivolatile compounds in chemical ionization GC-MS using a mass-to-structure (MTS) Search Engine with integral isotope pattern ranking.

    PubMed

    Liao, Wenta; Draper, William M

    2013-02-21

    The mass-to-structure or MTS Search Engine is an Access 2010 database containing theoretical molecular mass information for 19,438 compounds assembled from common sources such as the Merck Index, pesticide and pharmaceutical compilations, and chemical catalogues. This database, which contains no experimental mass spectral data, was developed as an aid to identification of compounds in atmospheric pressure ionization (API)-LC-MS. This paper describes a powerful upgrade to this database, a fully integrated utility for filtering or ranking candidates based on isotope ratios and patterns. The new MTS Search Engine is applied here to the identification of volatile and semivolatile compounds including pesticides, nitrosoamines and other pollutants. Methane and isobutane chemical ionization (CI) GC-MS spectra were obtained from unit mass resolution mass spectrometers to determine MH(+) masses and isotope ratios. Isotopes were measured accurately with errors of <4% and <6%, respectively, for A + 1 and A + 2 peaks. Deconvolution of interfering isotope clusters (e.g., M(+) and [M - H](+)) was required for accurate determination of the A + 1 isotope in halogenated compounds. Integrating the isotope data greatly improved the speed and accuracy of the database identifications. The database accurately identified unknowns from isobutane CI spectra in 100% of cases where as many as 40 candidates satisfied the mass tolerance. The paper describes the development and basic operation of the new MTS Search Engine and details performance testing with over 50 model compounds. PMID:23248816

  4. Fragmentation energy index for universalization of fragmentation energy in ion trap mass spectrometers for the analysis of chemical weapon convention related chemicals by atmospheric pressure ionization-tandem mass spectrometry analysis.

    PubMed

    Palit, Meehir; Mallard, Gary

    2009-04-01

    The use of mass spectra generated at 70 eV in electron ionization (EI) as a universal standard for EI has helped in the generation of searchable library databases and had a profound influence on the analytical applications of gas chromatography/mass spectrometry (GC/MS), similarly for liquid chromatography tandem mass spectrometry (LC-MS/MS), suggesting a novel method to normalize the collisional energy for the universalization of fragmentation energy for the analysis of Chemical Weapon Convention (CWC)-related chemicals by atmospheric pressure ionization-tandem mass spectrometry (API-MS(n)) using three-dimensional (3D) ion trap instruments. For normalizing fragmentation energy a "fragmentation energy index" (FEI) is proposed which is an arbitrary scale based on the fact of specific MS/MS fragmentation obtained at different collisional energies for the reference chemicals which are not CWC scheduled compounds. FEI 6 for the generation of an MS(n) library-searchable mass spectral database is recommended. PMID:19331429

  5. Liquid chromatographic-atmospheric pressure chemical ionization mass spectrometric analysis of opiates and metabolites in rat urine after inhalation of opium.

    PubMed

    Kikura-Hanajiri, R; Kaniwa, N; Ishibashi, M; Makino, Y; Kojima, S

    2003-06-01

    To examine the urinary excretion of opiates and their metabolites following inhalation exposure of rats to opium, analytical procedures for the simultaneous determination of the compounds in opium, the vapor derived by the volatilization of opium and the urine of rats exposed to the opium vapor were developed using liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS). Seven compounds were determined in the opium, namely morphine, codeine, thebaine, noscapine, papaverine, meconic acid and meconin. All seven were extracted with 2.5% acetic acid solution and subjected to LC-APCI-MS analysis. The separation was performed on an ODS column in acetonitrile-50 mM ammonium formate buffer (pH 3.0) using a linear gradient program and quantitative analysis was carried out in the selected ion monitoring mode ([M+H](+)). For the analysis of the volatilization of opium, the opium (1 g) was added to a glass pipe, which was then heated at 300 degrees C for 20 min. Negative pressure (air flow-rate; 300 ml/min) was used to draw the vapor through a series of glass wool and methanol traps. The total amount of each compound in the vapor was estimated by measurement of the compounds trapped in the glass wool and methanol. Wister rats (n=3) were exposed to the vapor derived from the volatilization system and the urinary amounts (0-72 h) of the six opiates and metabolites including morphine-3-grucronide (M3G) and morphine-6-grucronide (M6G) were measured after solid-phase extraction. The calibration curves for those compounds in the rat urine were linear over the concentration range 10-500 ng/ml. The recoveries for each analyte from the rat urine sample spiked with standard solution were generally greater than 80%, and the relative standard deviation for the analytical procedure was less than 8% with the exception of meconin. After inhalation exposure of rats to opium, M3G (5.45-14.38 micro g), morphine (2.27-4.65 micro g), meconin (0.54-1.85 micro g), codeine (0.54-1.85 micro g), noscapine (0.34-0.40 micro g) and papaverine (0.01-0.04 micro g) were detected in the urine over 72 h. However, only trace levels of thebaine were observed despite it being one of the major alkaloids found in the opium. On the other hand, a relatively large amount of meconin was detected in the vapor and the urine as compared with the opium. It is suggested that the presence of meconin in biological fluids could be indicative of opium ingestion by inhalation. PMID:12726852

  6. 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

  7. 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

  8. Pressurized liquid extraction and dispersive liquid-liquid microextraction for determination of tocopherols and tocotrienols in plant foods by liquid chromatography with fluorescence and atmospheric pressure chemical ionization-mass spectrometry detection.

    PubMed

    Viñas, Pilar; Bravo-Bravo, María; López-García, Ignacio; Pastor-Belda, Marta; Hernández-Córdoba, Manuel

    2014-02-01

    Pressurized liquid extraction (PLE) and dispersive liquid-liquid microextraction (DLLME) were used to isolate and preconcentrate tocopherols and tocotrienols from plant foods. The Taguchi experimental method was used to optimize the six factors (three levels for each factor), affecting DLLME, namely: carbon tetrachloride volume, methanol volume, aqueous sample volume, pH of sample, sodium chloride concentration and time of the centrifugation step. The influencing parameters selected were 2 mL of methanol:isopropanol (1:1) (disperser solvent), 150 µL carbon tetrachloride (extraction solvent) and 10 mL aqueous solution. The organic phase was injected into reversed-phase liquid chromatography (LC) with an isocratic mobile phase composed of an 85:15 (v/v) methanol:water mixture and a pentafluorophenyl stationary phase. Detection was carried out using both fluorescence and atmospheric pressure chemical ionization mass spectrometry (APCI-MS) in negative ion mode. Quantification was carried out by the standard addition method. Detection limits were in the range 0.2-0.3 ng mL(-1) for the vitamers with base-line resolution. The recoveries obtained using the optimized DLLME were in the 90-108% range, with RSDs lower than 6.7%. The APCI-MS spectra, in combination with fluorescence spectra, permitted the correct identification of compounds in the vegetable and fruit samples. The method was validated according to international guidelines and using two certified reference materials. PMID:24401390

  9. Optimization of Routine Identification of Clinically Relevant Gram-Negative Bacteria by Use of Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry and the Bruker Biotyper

    PubMed Central

    Ford, Bradley A.

    2013-01-01

    Matrix-assisted laser desorption ionization–time of flight mass spectrometry (MALDI-TOF MS) might complement and one day replace phenotypic identification of bacteria in the clinical microbiology laboratory, but there is no consensus standard regarding the requirements for its validation prior to clinical use in the United States. The objective of this study was to assess the preanalytical variables influencing Gram-negative identification by use of the Bruker Biotyper MALDI-TOF MS system, including density of organism spotting on a stainless steel target plate and the direct overlay of organisms with formic acid. A heavy smear with formic acid overlay was either superior or equivalent to alternative smear conditions. Microbiological preanalytical variables were also assayed, such as culture medium, growth temperature, and use of serial subculture. Postanalytical analysis included the application of modified species-level identification acceptance criteria. Biotyper identifications were compared with those using traditional phenotypic methods, and discrepancies were resolved with 16S rRNA gene sequencing. Compared to the recommended score cutoffs of the manufacturer, the application of optimized Biotyper score cutoffs for species-level identification increased the rate of identification by 6.75% for the enteric Gram-negative bacteria and 4.25% for the nonfermenting Gram-negative bacteria. Various incubation temperatures, growth medium types, and repeat subcultures did not result in misidentification. We conclude that the Bruker MALDI Biotyper is a robust system for the identification of Gram-negative organisms in the clinical laboratory and that meaningful performance improvements can be made by implementing simple pre- and postanalytical techniques. PMID:23426923

  10. Comparison of Bruker Biotyper Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometer to BD Phoenix Automated Microbiology System for Identification of Gram-Negative Bacilli?

    PubMed Central

    Saffert, Ryan T.; Cunningham, Scott A.; Ihde, Sherry M.; Monson Jobe, Kristine E.; Mandrekar, Jayawant; Patel, Robin

    2011-01-01

    We compared the BD Phoenix automated microbiology system to the Bruker Biotyper (version 2.0) matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry (MS) system for identification of Gram-negative bacilli, using biochemical testing and/or genetic sequencing to resolve discordant results. The BD Phoenix correctly identified 363 (83%) and 330 (75%) isolates to the genus and species level, respectively. The Bruker Biotyper correctly identified 408 (93%) and 360 (82%) isolates to the genus and species level, respectively. The 440 isolates were grouped into common (308) and infrequent (132) isolates in the clinical laboratory. For the 308 common isolates, the BD Phoenix and Bruker Biotyper correctly identified 294 (95%) and 296 (96%) of the isolates to the genus level, respectively. For species identification, the BD Phoenix and Bruker Biotyper correctly identified 93% of the common isolates (285 and 286, respectively). In contrast, for the 132 infrequent isolates, the Bruker Biotyper correctly identified 112 (85%) and 74 (56%) isolates to the genus and species level, respectively, compared to the BD Phoenix, which identified only 69 (52%) and 45 (34%) isolates to the genus and species level, respectively. Statistically, the Bruker Biotyper overall outperformed the BD Phoenix for identification of Gram-negative bacilli to the genus (P < 0.0001) and species (P = 0.0005) level in this sample set. When isolates were categorized as common or infrequent isolates, there was statistically no difference between the instruments for identification of common Gram-negative bacilli (P > 0.05). However, the Bruker Biotyper outperformed the BD Phoenix for identification of infrequently isolated Gram-negative bacilli (P < 0.0001). PMID:21209160

  11. 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.

  12. Potential of gas chromatography-atmospheric pressure chemical ionization-time-of-flight mass spectrometry for the determination of sterols in human plasma.

    PubMed

    Matysik, S; Schmitz, G; Bauer, S; Kiermaier, J; Matysik, F-M

    2014-04-11

    The application of Gas Chromatography (GC)-Atmospheric Pressure Chemical Ionization (APCI)-Time-of-Flight Mass Spectrometry (TOF-MS) is presented for sterol analysis in human plasma. A commercial APCI interface was modified to ensure a well-defined humidity which is essential for controlled ionization. In the first step, optimization regarding flow rates of auxiliary gases was performed by using a mixture of model analytes. Secondly, the qualitative and quantitative analysis of sterols including oxysterols, cholesterol precursors, and plant sterols as trimethylsilyl-derivatives was successfully carried out. The characteristics of APCI together with the very good mass accuracy of TOF-MS data enable the reliable identification of relevant sterols in complex matrices. Linear calibration lines and plausible results for healthy volunteers and patients could be obtained whereas all mass signals were extracted with an extraction width of 20 ppm from the full mass data set. One advantage of high mass accuracy can be seen in the fact that from one recorded run any search for m/z can be performed. PMID:24463103

  13. Fast determination of 3-ethenylpyridine as a marker of environmental tobacco smoke at trace level using direct atmospheric pressure chemical ionization tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Jiang, Cheng-Yong; Sun, Shi-Hao; Zhang, Qi-Dong; Liu, Jun-Hui; Zhang, Jian-Xun; Zong, Yong-Li; Xie, Jian-Ping

    2013-03-01

    A method with atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS) was developed and applied to direct analysis of Environmental Tobacco Smoke (ETS), using 3-ethenylpyridine (3-EP) as a vapour-phase marker. In this study, the ion source of APCI-MS/MS was modified and direct analysis of gas sample was achieved by the modified instrument. ETS samples were directly introduced, via an atmospheric pressure inlet, into the APCI source. Ionization was carried out in positive-ion APCI mode and 3-EP was identified by both full scan mode and daughter scan mode. Quantification of 3-EP was performed by multiple reaction monitoring (MRM) mode. The calibration curve was obtained in the range of 1-250 ng L-1 with a satisfactory regression coefficient of 0.999. The limit of detection (LOD) and the limit of quantification (LOQ) were 0.5 ng L-1 and 1.6 ng L-1, respectively. The precision of the method, calculated as relative standard deviation (RSD), was characterized by repeatability (RSD 3.92%) and reproducibility (RSD 4.81%), respectively. In real-world ETS samples analysis, compared with the conventional GC-MS method, the direct APCI-MS/MS has shown better reliability and practicability in the determination of 3-EP at trace level. The developed method is simple, fast, sensitive and repeatable; furthermore, it could provide an alternative way for the determination of other volatile pollutants in ambient air at low levels.

  14. 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

  15. Characterization of triacylglycerol and diacylglycerol composition of plant oils using high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Holcapek, Michal; Jandera, Pavel; Zderadicka, Petr; Hrubá, Lucie

    2003-08-29

    Triacylglycerols (TGs) and diacylglycerols (DGs) in 16 plant oil samples (hazelnut, pistachio, poppy-seed, almond, palm, Brazil-nut, rapeseed, macadamia, soyabean, sunflower, linseed, Dracocephalum moldavica, evening primrose, corn, amaranth, Silybum arianum) were analyzed by HPLC-MS with atmospheric pressure chemical ionization (APCI) and UV detection at 205 nm on two Nova-Pak C18 chromatographic columns connected in series. A single chromatographic column and non-aqueous ethanol-acetonitrile gradient system was used as a compromise between the analysis time and the resolution for the characterization of TG composition of five plant oils. APCI mass spectra were applied for the identification of all TGs and other acylglycerols. The isobaric positional isomers can be distinguished on the basis of different relative abundances of the fragment ions formed by preferred losses of the fatty acid from sn-1(3) positions compared to the sn-2 position. Excellent chromatographic resolution and broad retention window together with APCI mass spectra enabled positive identification of TGs containing fatty acids with odd numbers of carbon atoms such as margaric (C17:0) and heptadecanoic (C17:1) acids. The general fragmentation patterns of TGs in both APCI and electrospray ionization mass spectra were proposed on the basis of MSn spectra measured with an ion trap analyzer. The relative concentrations of particular TGs in the analyzed plant oils were estimated on the basis of relative peak areas measured with UV detection at 205 nm. PMID:12974290

  16. Negative atmospheric pressure chemical ionisation low-energy collision activation mass spectrometry for the characterisation of flavonoids in extracts of fresh herbs

    Microsoft Academic Search

    Ulla Justesen

    2000-01-01

    The flavonoid composition of commonly eaten fresh herbs such as dill, oregano and parsley was analysed by combined LC, MS and low-energy collision induced dissociation (CID) MS–MS. Negative atmospheric pressure chemical ionisation (APCI) MS and MS–MS were used to provide molecular mass information and product-ion spectra of the glycosyl compounds. The most prominent fragment was found to arise from the

  17. Preparation of negative electrodes for lithium-ion rechargeable battery by pressure-pulsed chemical vapor infiltration of pyrolytic carbon into electro-conductive forms

    Microsoft Academic Search

    Yoshimi Ohzawa; Masami Mitani; Takako Suzuki; Vinay Gupta; Tsuyoshi Nakajima

    2003-01-01

    The plate-type negative electrodes for lithium-ion rechargeable battery were prepared by pressure-pulsed chemical vapor infiltration of pyrolytic carbon (pyrocarbon) into two sorts of conductive porous forms, that is, the carbonized paper (A) and the TiN-coated paper (B), as the conductive fillers and\\/or current collectors. The electrodes had the three-dimensionally continuous current paths in the pyrocarbon-based anodes without the organic binders

  18. Quantitation of fourteen urinary alpha-amino acids using isobutane gas chromatography chemical ionization mass spectrometry with 13C amino acids as internal standards.

    PubMed

    Finlayson, P J; Christopher, R K; Duffield, A M

    1980-10-01

    Isobutane chemical ionization gas chromatography mass spectometry of the N-trifluoroacetyl-carboxy-n-butyl ester derivatives of amino acids, using a commercial per-13C-amino acid mixture as internal standards, provided a sensitive and specific method for quantitative analysis of fourteen urinary alpha-amino acids. A computer controlled quadrupole mass spectrometer was used in a selected ion monitoring mode to record the ion current due to the protonated molecular ions of each alpha-amino acid/13C analogue pair. BASIC programmes located peak maxima, and using previously established standard curves, calculated the amino acid content on the bases of both peak height and peak area ratios. Duplicate amino acid analyses are possible on 5 microliter of urine. Instrumental analysis required 25 minutes, automated data processing 10 minutes, and sample preparation 2 hours. Detection limits approached 1 ng with a typical mean standard deviation of 2% for the instrumental analysis. PMID:6452181

  19. Identification of nonprotein amino acids from cycad seeds as N-ethoxycarbonyl ethyl ester derivatives by positive chemical-ionization gas chromatography-mass spectrometry.

    PubMed

    Pan, M; Mabry, T J; Cao, P; Moini, M

    1997-11-01

    Nonprotein amino acids from nine species of cycad seeds were analyzed as N-ethoxycarbonyl ethyl ester (ECEE) derivatives by positive chemical-ionization gas chromatography-mass spectrometry. Based on the retention times and mass spectrometry analyses, 12 nonprotein amino acids were identified in these seeds. In addition to the excitatory and putative neurotoxin beta-N-methylamino-L-alanine (BMAA), the known neurotoxin beta-N-oxalylamino-L-alanine (BOAA) was detected from the seeds of Macrozamia moorei and M. communis, and delta-N-oxalyl-ornithine was obtained from the Cycas revoluta seeds. A novel nonprotein amino acid named cycasindene, previously reported from C. revoluta, was also found in the seeds of members of the C. angulata and C. rumphii complex. Eight additional known nonprotein amino acids were also identified. This is the first report of the neurotoxin BOAA from cycad seeds. PMID:9409004

  20. High-throughput walkthrough detection portal for counter terrorism: detection of triacetone triperoxide (TATP) vapor by atmospheric-pressure chemical ionization ion trap mass spectrometry.

    PubMed

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

    2011-09-15

    With the aim of improving security, a high-throughput portal system for detecting triacetone triperoxide (TATP) vapor emitted from passengers and luggage was developed. The portal system consists of a push-pull air sampler, an atmospheric-pressure chemical ionization (APCI) ion source, and an explosives detector based on mass spectrometry. To improve the sensitivity of the explosives detector, a novel linear ion trap mass spectrometer with wire electrodes (wire-LIT) is installed in the portal system. TATP signals were clearly obtained 2?s after the subject under detection passed through the portal system. Preliminary results on sensitivity and throughput show that the portal system is a useful tool for preventing the use of TATP-based improvised explosive devices by screening persons in places where many people are coming and going. PMID:21818804

  1. Determination of gamma-hydroxybutyric acid (GHB) in plasma and urine by headspace solid-phase microextraction and gas chromatography/positive ion chemical ionization mass spectrometry.

    PubMed

    Frison, G; Tedeschi, L; Maietti, S; Ferrara, S D

    2000-01-01

    A new method for the qualitative and quantitative analysis of gamma-hydroxybutyric acid (GHB) in plasma and urine samples is described. It involves the conversion of GHB to gamma-butyrolactone (GBL), its subsequent headspace solid-phase microextraction (SPME), and detection by gas chromatography/positive ion chemical ionization mass spectrometry (GC/PICI-MS), using D(6)-GBL as internal standard. The assay is linear over a plasma GHB range of 1-100 microg/mL (n = 5, r = 0.999) and a urine GHB range of 5-150 microg/mL (n = 5, r = 0. 998). Relative intra- and inter-assay standard deviations, determined for plasma and urine samples at 5 and 50 microg/mL, are all below 5%. The method is simple, specific and reasonably fast. It may be applied for clinical and forensic toxicology as well as for purposes of therapeutic drug monitoring. PMID:11114057

  2. A preconcentrator coupled to a GC/FTMS: advantages of self-chemical ionization, mass measurement accuracy, and high mass resolving power for GC applications.

    PubMed

    Solouki, Touradj; Szulejko, Jan E; Bennett, Justin B; Graham, LeRae B

    2004-08-01

    Coupling of a cryogenic preconcentrator (PC) to a gas chromatograph/Fourier transform ion cyclotron resonance mass spectrometer (GC/FT-ICR MS) is reported. To demonstrate the analytical capabilities of the PC/GC/FT-ICR MS, headspace samples containing volatile organic compounds (VOCs) emitted from detached pine tree twigs were analyzed. Sub-ppm mass measurement accuracy (MMA) for highly resolved (m/Deltam(50%) > 150 k) terpene ions was achieved. Direct PC/GC/FT-ICR MS analyses revealed that detached twigs from pine trees emit acetone, camphor, and four detectable hydrocarbon isomers with C(10)H(16) empirical formula. The unknown analytes were identified based on accurate mass measurement and their mass spectral appearances. Authentic samples were used to confirm initially unknown identifications. Self-chemical-ionization (SCI) reactions furnished an additional dimension for rapid isomer differentiation of GC eluents in real time. PMID:15276166

  3. Application of high-resolution time-of-flight chemical ionization mass spectrometry measurements to estimate volatility distributions of ?-pinene and naphthalene oxidation products

    NASA Astrophysics Data System (ADS)

    Chhabra, P. S.; Lambe, A. T.; Canagaratna, M. R.; Stark, H.; Jayne, J. T.; Onasch, T. B.; Davidovits, P.; Kimmel, J. R.; Worsnop, D. R.

    2015-01-01

    Recent developments in high-resolution time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) have made it possible to directly detect atmospheric organic compounds in real time with high sensitivity and with little or no fragmentation, including low-volatility, highly oxygenated organic vapors that are precursors to secondary organic aerosol formation. Here, using ions identified by high-resolution spectra from an HR-ToF-CIMS with acetate reagent ion chemistry, we develop an algorithm to estimate the vapor pressures of measured organic acids. The algorithm uses identified ion formulas and calculated double bond equivalencies, information unavailable in quadrupole CIMS technology, as constraints for the number of possible oxygen-containing functional groups. The algorithm is tested with acetate chemical ionization mass spectrometry (acetate-CIMS) spectra of O3 and OH oxidation products of ?-pinene and naphthalene formed in a flow reactor with integrated OH exposures ranged from 1.2 × 1011 to 9.7 × 1011 molec s cm-3, corresponding to approximately 1.0 to 7.5 days of equivalent atmospheric oxidation. Measured gas-phase organic acids are similar to those previously observed in environmental chamber studies. For both precursors, we find that acetate-CIMS spectra capture both functionalization (oxygen addition) and fragmentation (carbon loss) as a function of OH exposure. The level of fragmentation is observed to increase with increased oxidation. The predicted condensed-phase secondary organic aerosol (SOA) average acid yields and O/C and H/C ratios agree within uncertainties with previous chamber and flow reactor measurements and ambient CIMS results. While acetate reagent ion chemistry is used to selectively measure organic acids, in principle this method can be applied to additional reagent ion chemistries depending on the application.

  4. Computational tests of quantum chemical models for excited and ionized states of molecules with phosphorus and sulfur atoms.

    PubMed

    Hahn, David K; RaghuVeer, Krishans; Ortiz, J V

    2014-05-15

    Time-dependent density functional theory (TD-DFT) and electron propagator theory (EPT) are used to calculate the electronic transition energies and ionization energies, respectively, of species containing phosphorus or sulfur. The accuracy of TD-DFT and EPT, in conjunction with various basis sets, is assessed with data from gas-phase spectroscopy. TD-DFT is tested using 11 prominent exchange-correlation functionals on a set of 37 vertical and 19 adiabatic transitions. For vertical transitions, TD-CAM-B3LYP calculations performed with the MG3S basis set are lowest in overall error, having a mean absolute deviation from experiment of 0.22 eV, or 0.23 eV over valence transitions and 0.21 eV over Rydberg transitions. Using a larger basis set, aug-pc3, improves accuracy over the valence transitions via hybrid functionals, but improved accuracy over the Rydberg transitions is only obtained via the BMK functional. For adiabatic transitions, all hybrid functionals paired with the MG3S basis set perform well, and B98 is best, with a mean absolute deviation from experiment of 0.09 eV. The testing of EPT used the Outer Valence Green's Function (OVGF) approximation and the Partial Third Order (P3) approximation on 37 vertical first ionization energies. It is found that OVGF outperforms P3 when basis sets of at least triple-? quality in the polarization functions are used. The largest basis set used in this study, aug-pc3, obtained the best mean absolute error from both methods -0.08 eV for OVGF and 0.18 eV for P3. The OVGF/6-31+G(2df,p) level of theory is particularly cost-effective, yielding a mean absolute error of 0.11 eV. PMID:24779512

  5. 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

  6. Measuring Air-Ionizer Output

    NASA Technical Reports Server (NTRS)

    Lonborg, J. O.

    1985-01-01

    Test apparatus checks ion content of airstream from commercial air ionizer. Apparatus ensures ion output is sufficient to neutralize static charges in electronic assembly areas and concentrations of positive and negative ions are balanced.

  7. Negative ion ultraviolet matrix-assisted laser desorption ionization mass spectrometry and post source decay of glycosyl esters of nucleoside pyrophosphates*

    PubMed Central

    Heinrich, Maria; Schäffer, Christina; Messner, Paul; Allmaier, Günter

    2015-01-01

    Six different glycosyl esters of nucleoside pyrophosphates (monosaccharide nucleotides) were analyzed by means of matrix-assisted laser desorption/ionisation reflectron time-of-flight mass spectrometry (MALDI/RToF MS) in the negative ion mode. Several matrices were evaluated and 3-hydroxypicolinic acid as well as ?-cyano-4-hydroxycinnamic acid (CHCA) turned out to be the matrices of choice applying the thin layer technique to obtain maximum sensitivity for deprotonated molecular ion detection and maximal fragmentation particular with CHCA. The determination of the molecular mass with a mass accuracy below 0.1% was feasible with sample amounts in the lower femtomole range applying a MALDI desk-top mass spectrometer. A further important refinement of this technique was the use of post source decay (PSD) fragment ion analysis with a curved field reflector (which means no stepping of the reflector voltage). Detailed structural information of the six selected monosaccharide nucleotides could be obtained with PSD and differences in the fragmentation pattern were used to distinguish them. This method (based on molecular mass and PSD fragment ion analysis) has been applied to verify the presence of a glycosyl ester of nucleoside pyrophosphate in samples from Saccharomyces cerevisiae. PMID:19136728

  8. 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

    reactor used for diamond chemical vapour deposition (CVD). Parameters varied include the hydrocarbon (CH4 to reinforce the consensus view that H atom production during diamond CVD in a hot ®lament reactor arises as a result of dissociative adsorption on the hot ®lament surface, whereas CH3 radical formation is dominated

  9. 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…

  10. 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

  11. Basic Vapor Exposure for Tuning the Charge State Distribution of Proteins in Negative Electrospray Ionization: Elucidation of Mechanisms by Fluorescence Spectroscopy

    NASA Astrophysics Data System (ADS)

    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.

  12. Visualizing the Positive-Negative Interface of Molecular Electrostatic Potentials as an Educational Tool for Assigning Chemical Polarity

    ERIC Educational Resources Information Center

    Schonborn, Konrad; Host, Gunnar; Palmerius, Karljohan

    2010-01-01

    To help in interpreting the polarity of a molecule, charge separation can be visualized by mapping the electrostatic potential at the van der Waals surface using a color gradient or by indicating positive and negative regions of the electrostatic potential using different colored isosurfaces. Although these visualizations capture the molecular…

  13. 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

  14. Method validation for the analysis of 169 pesticides in soya grain, without clean up, by liquid chromatography-tandem mass spectrometry using positive and negative electrospray ionization.

    PubMed

    Pizzutti, Ionara R; de Kok, André; Zanella, Renato; Adaime, Martha B; Hiemstra, Maurice; Wickert, Cristine; Prestes, Osmar D

    2007-02-23

    Part of a comprehensive study on the comparison of different extraction methods, GC-MS(/MS) and LC-MS/MS detection methods and modes, for the analysis of soya samples is described in this paper. The validation of an acetone-based extraction method for analysis of 169 pesticides in soya, using LC-MS/MS positive and negative electrospray ionisation (ESI) mode, is reported. Samples (5 g) were soaked with 10 g water and subsequently extracted with 100 mL of a mixture of acetone, dichloromethane and light petroleum (1:1:1), in the presence of 15 g anhydrous sodium sulphate. After centrifugation, aliquots of the extract were evaporated and reconstituted in 1.0 mL of methanol, before direct injection of the final extract (corresponding with 0.05 g soya mL(-1)) into the LC-MS/MS system. Linearity, r(2) of calibration curves, instrument limit of detection/quantitation (LOD/LOQ) and matrix effect were evaluated, based on seven concentrations measured in 6-fold. Good linearity (at least r(2)> or =0.99) of the calibration curves was obtained over the range from 0.1 or 0.25 to 10.0 ng mL(-1), corresponding with pesticide concentrations in soya bean extract of 2 or 5-200 microg kg(-1). Instrument LOD values generally were 0.1 or 0.25 ng mL(-1). Matrix effects were negligible for approximately 90% of the pesticides. The accuracy, precision and method LOQ were determined via recovery experiments, spiking soya at 10, 50, 100 microg kg(-1), six replicates per level. In both ESI modes, method LOQ values were mostly 10 or 50 microg kg(-1) and more than 70% of pesticides analysed by each mode met the acceptability criteria of recovery (70-120%) and RSD (< or =20%), at one or more of the three levels studied. A fast, easy and efficient method with acceptable performance was achieved for a difficult matrix as soya, without cleanup. PMID:17222861

  15. Kelvin spray ionization.

    PubMed

    Özdemir, Abdil; Lin, Jung-Lee; Gillig, Kent J; Chen, Chung-Hsuan

    2013-11-21

    A novel self-powered dual spray ionization source has been developed for applications in mass spectrometry. This new source does not use any power supply and produces both positive and negative ions simultaneously. The idea behind this ionization source comes from the Kelvin water dropper. The source employs one or two syringes, two pneumatic sprays operated over a range of flow rates (0.15-15 ?L min(-1)) and gas pressures (0-150 psi), and two double layered metal screens for ion formation. A variable electrostatic potential from 0 to 4 kV can be produced depending on solvent and gas flow rates that allow gentle ionization of compounds. There are several parameters that affect the performance during ionization of molecules including the flow rate of solvent, gas pressure, solvent acidity, position of spray and metal screens with respect to each other and distance between metal screens and the counter electrode. This ionization method has been successfully applied to solutions of peptides, proteins and non-covalent complexes. In comparison with ESI, the charge number of the most populated state is lower than that from ESI. It indicates that this is a softer ionization technique and it produces more protein ions with folded structures. The unique features of Kelvin spray ionization (KeSI) are that the method is self-powered and ionization occurs at very low potentials by providing very low internal energy to the ions. This advantage can be used for the ionization of very fragile molecules and investigation of non-covalent interactions. PMID:24080942

  16. Measurement of low-ppm mixing ratios of water vapor in the upper troposphere and lower stratosphere using chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Thornberry, T. D.; Rollins, A. W.; Gao, R. S.; Watts, L. A.; Ciciora, S. J.; McLaughlin, R. J.; Voigt, C.; Hall, B.; Fahey, D. W.

    2013-06-01

    A chemical ionization mass spectrometer (CIMS) instrument has been developed for the fast, precise, and accurate measurement of water vapor (H2O) at low mixing ratios in the upper troposphere and lower stratosphere (UT/LS). A low-pressure flow of sample air passes through an ionization volume containing an ?-particle radiation source, resulting in a cascade of ion-molecule reactions that produce hydronium ions (H3O+) from ambient H2O. The production of H3O+ ions from ambient H2O depends on pressure and flow through the ion source, which were tightly controlled in order to maintain the measurement sensitivity independent of changes in the airborne sampling environment. The instrument was calibrated every 45 min in flight by introducing a series of H2O mixing ratios between 0.5 and 153 parts per million (ppm, 10-6 mol mol-1) generated by Pt-catalyzed oxidation of H2 standards while overflowing the inlet with dry synthetic air. The CIMS H2O instrument was deployed in an unpressurized payload area aboard the NASA WB-57F high-altitude research aircraft during the Mid-latitude Airborne Cirrus Properties Experiment (MACPEX) mission in March and April 2011. The instrument performed successfully during seven flights, measuring H2O mixing ratios below 5 ppm in the lower stratosphere at altitudes up to 17.7 km, and as low as 3.5 ppm near the tropopause. Data were acquired at 10 Hz and reported as 1 s averages. In-flight calibrations demonstrated a typical sensitivity of 2000 Hz ppm-1 at 3 ppm with a signal to noise ratio (2 ?, 1 s) greater than 32. The total measurement uncertainty was 9 to 11%, derived from the uncertainty in the in situ calibrations.

  17. Measurement of low-ppm mixing ratios of water vapor in the upper troposphere and lower stratosphere using chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Thornberry, T. D.; Rollins, A. W.; Gao, R. S.; Watts, L. A.; Ciciora, S. J.; McLaughlin, R. J.; Voigt, C.; Hall, B.; Fahey, D. W.

    2013-01-01

    A chemical ionization mass spectrometer (CIMS) instrument has been developed for the fast, precise, and accurate measurement of water vapor (H2O) at low mixing ratios in the upper troposphere and lower stratosphere (UT/LS). A low-pressure flow of sample air passes through an ionization volume containing an ?-particle radiation source, resulting in a cascade of ion-molecule reactions that produce hydronium ions (H3O+) from ambient H2O. The production of H3O+ ions from ambient H2O depends on pressure and flow through the ion source, which were tightly controlled in order to maintain the measurement sensitivity independent of changes in the airborne sampling environment. The instrument was calibrated every 45 min in flight by introducing a series of H2O mixing ratios between 0.5 and 153 parts per million (ppm) generated by Pt-catalyzed oxidation of H2 standards while overflowing the inlet with dry synthetic air. The CIMS H2O instrument was deployed in an unpressurized payload area aboard the NASA WB-57 high altitude research aircraft during the Mid-latitude Airborne Cirrus Properties Experiment (MACPEX) mission in March and April 2011. The instrument performed successfully during seven flights, measuring H2O mixing ratios below 5 ppm in the lower stratosphere at altitudes up to 17.7 km, and as low as 3.5 ppm near the tropopause. Data were acquired at 10 Hz and reported as 1-s averages. In-flight calibrations demonstrated a typical sensitivity of 2000 Hz ppm-1 at 3 ppm with a signal to noise ratio (2?, 1-s) greater than 32. The total measurement uncertainty was 9 to 11%, derived from the uncertainty in the in situ calibrations.

  18. Highly sensitive and selective analysis of urinary steroids by comprehensive two-dimensional gas chromatography combined with positive chemical ionization quadrupole mass spectrometry

    PubMed Central

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

    2014-01-01

    Comprehensive two dimensional gas chromatography (GC×GC) provides greater separation space than conventional GC. Because of fast peak elution, a time of flight mass spectrometer (TOFMS) is the usual structure-specific detector of choice. The quantitative capabilities of a novel GC×GC fast quadrupole MS were investigated with electron ionization (EI), and CH4 or NH3 positive chemical ionization (PCI) for analysis of endogenous urinary steroids targeted in anti-doping tests. Average precisions for steroid quantitative analysis from replicate urine extractions were 6% (RSD) for EI and 8% for PCI-NH3. The average limits of detection (LOD) calculated by quantification ions for 12 target steroids spiked into steroid-free urine matrix (SFUM) were 2.6 ng mL?1 for EI, 1.3 ng mL?1 for PCI-CH4, and 0.3 ng mL?1 for PCI-NH3, all in mass scanning mode. The measured limits of quantification (LOQ) with full mass scan GC×GC-qMS were comparable with the LOQ values measured by one-dimensional GC-MS in single ion monitoring (SIM) mode. PCI-NH3 yields fewer fragments and greater (pseudo)molecular ion abundances than EI or PCI-CH4. These data show a benchtop GC×GC-qMS system has the sensitivity, specificity, and resolution to analyze urinary steroids at normal urine concentrations, and that PCI-NH3, not currently available on most GC×GC-TOFMS instruments, is of particular value for generation of structure-specific ions. PMID:22606686

  19. Chemical Ionization Mass Spectrometry-Based Measurements of HO2 and RO2 During TRACE-P

    NASA Technical Reports Server (NTRS)

    Cantrell, Christopher A.; Eisele, Fred L.

    2004-01-01

    The Transport and Chemical Evolution over the Pacific (TRACE-P) mission extends NASA's Global Tropospheric Experiment (GTE) series of campaigns. TRACE-P was an aircraft-based campaign that was part of a larger ground-based and aircraft-based program (APARE) under the auspices of the International Global Atmospheric Chemistry (IGAC) program. TRACE-P was designed to (1) determine the chemical composition of Asian outflow over the western Pacific, and to (2) determine the chemical evolution of the Asian outflow. These objectives were addressed through a variety of observations and numerical modeling exercises. In particular, the goals included sampling strategies that would improve understanding of the budgets of odd hydrogen species (OH and HO2), budgets of NOx (NO, NO2, and their reservoirs), and impacts of oxidants produced in the outflow on air quality in the United States. The NASA DC-8 and P-3B aircraft were deployed in the March and April, 2001 out of primary bases of operation in Hong Kong and Yokota Air Base in Japan. These two aircraft have complementary capabilities which allow high altitude and long range impacts, as well as low altitude, local impacts to be assessed. In order to quantify the composition and evolution of Asian outflow, it is important to quantify as many species as possible including photochemically active species (e.g. NO2, CH2O, O3, acetone, etc.), sources species (VOCs, CO, NOx, SO2, aerosols), reactive intermediates including free radicals (OH, HO2, RO2, and their reservoirs), and end products (nitric acid, sulfuric acid, secondary aerosols, etc.). The more complete the measurement suite, the more tightly constrained the numerical modeling can be (within the uncertainties of the measurements). The numerical models range in sophistication from simple steady state box models (as employed in this study) to multi-dimensional chemical transport models. Data were collected on approximately 20 flights of the DC-8 and 21 flights of the P-3B. Observations from both aircraft were used in the present analysis, but primarily focused on the P-3B flights since that was the platform on which the peroxy radical instrumentation was based.

  20. 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

  1. Amorphous silicon ionizing particle detectors

    DOEpatents

    Street, R.A.; Mendez, V.P.; Kaplan, S.N.

    1988-11-15

    Amorphous silicon ionizing particle detectors having a hydrogenated amorphous silicon (a--Si:H) thin film deposited via plasma assisted chemical vapor deposition techniques are utilized to detect the presence, position and counting of high energy ionizing particles, such as electrons, x-rays, alpha particles, beta particles and gamma radiation. 15 figs.

  2. Amorphous silicon ionizing particle detectors

    DOEpatents

    Street, Robert A. (Palo Alto, CA); Mendez, Victor P. (Berkeley, CA); Kaplan, Selig N. (El Cerrito, CA)

    1988-01-01

    Amorphous silicon ionizing particle detectors having a hydrogenated amorphous silicon (a--Si:H) thin film deposited via plasma assisted chemical vapor deposition techniques are utilized to detect the presence, position and counting of high energy ionizing particles, such as electrons, x-rays, alpha particles, beta particles and gamma radiation.

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

    PubMed

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

    2015-03-25

    A new method for simultaneous determination of phentermine and topiramate by liquid chromatography/electrospray tandem mass spectrometry (LC/MS/MS) operated in positive and negative ionization switching modes was developed and validated. Protein precipitation with acetonitrile was selected for sample preparation. Analyses were performed on a liquid chromatography system employing a Kromasil 60-5CN column (2.1mm×100mm, 5?m) and an isocratic elution with mixed solution of acetonitrile-20mM ammonium formate containing 0.3% formic acid (40:60, v/v), at a flow rate of 0.35mL/min. Doxazosin mesylate and pioglitazone were used as the internal standard (IS) respectively for quantification. The determination was carried out on an API 4000 triple-quadrupole mass spectrometer operated in multiple reaction monitoring (MRM) mode using the following transitions monitored simultaneously: positive m/z 150.0/91.0 for phentermine, m/z 452.1/344.3 for doxazosin, and negative m/z 338.3/77.9 for topiramate, m/z 355.0/41.9 for pioglitazone. The method was validated to be linear over the concentration range of 1-800ngmL(-1) for phentermine, 1-1000ngmL(-1) for topiramate. Within- and between-day accuracy and precision of the validated method at three different concentration levels were within the acceptable limits of <15% at all concentrations. Blood samples were collected into heparinized tubes before and after administration. The simple and robust LC/MS/MS method was successfully applied for the simultaneous determination of phentermine and topiramate in a pharmacokinetic study in healthy male Chinese volunteers. PMID:25668796

  4. 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.

  5. 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.

  6. Negative ion source

    DOEpatents

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

    1982-08-06

    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.

  7. Development and validation of a sensitive method for simultaneous determination of rosuvastatin and N-desmethyl rosuvastatin in human plasma using liquid chromatography/negative electrospray ionization/tandem mass spectrometry.

    PubMed

    Lee, H K; Ho, C S; Hu, M; Tomlinson, B; Wong, C K

    2013-11-01

    A sensitive and specific liquid chromatography tandem mass spectrometric method was developed and validated for the simultaneous determination of rosuvastatin (ROS) and N-desmethyl rosuvastatin (NOR-ROS) in human plasma using deuterium-labeled internal standards. The plasma samples were prepared using liquid-liquid extraction with diethyl ether. Chromatographic separation was accomplished on an Xterra MS C18 column. The mobile phase consisted of a gradient mixture of 15?µmol/L ammonium acetate in water and in methanol, maintained at a flow rate of 0.4?mL/min. Mass spectrometric detection was carried out in negative electrospray ionization mode and monitored by quantification and qualification transitions for each analyte. Using 300 ?L plasma samples, the lower limits of quantification of ROS and NOR-ROS were 0.05 and 0.02?µg/L respectively. The linearity of ROS and NOR-ROS ranged from 0.05 to 42 and 0.02 to 14?µg/L respectively. The relative standard deviations of ROS and NOR-ROS were <13 and 9%, respectively, while the deviations from expected values were within -4.7-9.8 and -5.2-4.6%, respectively. The present method offered high sensitivity and was successfully applied to a 24?h pharmacokinetic study of ROS and NOR-ROS in healthy subjects receiving a single dose of 10?mg ROS. PMID:23722358

  8. Remote sensing of chemical and physical processes in the atmosphere caused by the presence of radioactive ionization source

    NASA Astrophysics Data System (ADS)

    Boyarchuk, Kirill; Tumanov, Mikhail; Karelin, Alexander

    During the years of the nuclear power industry, some large accidents occurred at the nuclear objects, and that caused enormous environmental contamination. The last accident at the Fucushima-1 power plant highlighted the need to review seriously the safety issues at the active power plants and to develop the new effective methods for remote detection and control over radioactive environmental contamination and over general geophysical situation in the areas. The main influence of the fission products on the environment is its ionisation, and therefore various detectable biological and physical processes that are caused by ions. Presence of an ionisation source within the area under study may cause significant changes of absolute humidity and, that is especially important, changes of the chemical potential of atmosphere vapours indicating presence of charged condensation centres. These effects may cause anomalies in the IR radiation emitted from the Earth surface and jumps in the chemical potentials of water vapours that may be observed by means of the satellite remote sensing by specialized equipment (works by Dimitar Ouzounov, Sergey Pulinets, e.a.). In the current study, the theoretical description is presented from positions of the molecular-kinetic condensation theory that shows significant changes of the absolute and relative humidity values in the near-earth air layer. The detailed calculations of the water vapours in atmosphere were carried out with use of detailed non-stationary kinetic model of moist atmosphere air. The processes of condensation and evaporation were effectively considered with use of reactions of neutral water molecules’ association under presence of a third particle, conversion of water molecules with an ion cluster to a more complicated cluster, and the relevant counter reactions’ splits of neutral and ion clusters.

  9. 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

  10. 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

  11. 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.

  12. Secondary ion counting for surface-sensitive chemical analysis of organic compounds using time-of-flight secondary ion mass spectroscopy with cluster ion impact ionization

    SciTech Connect

    Hirata, K. [National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565 (Japan); Saitoh, Y.; Chiba, A.; Yamada, K. [Takasaki Advanced Radiation Research Institute (TARRI), Japan Atomic Energy Agency (JAEA), Takasaki Gumma 370-1292 (Japan); Takahashi, Y.; Narumi, K. [Advanced Science Research Center, Japan Atomic Energy Agency (JAEA), Takasaki, Gumma 370-1292 (Japan)

    2011-03-15

    We report suitable secondary ion (SI) counting for surface-sensitive chemical analysis of organic compounds using time-of-flight (TOF) SI mass spectroscopy, based on considerably higher emission yields of SIs induced by cluster ion impact ionization. A SI counting system for a TOF SI mass spectrometer was developed using a fast digital storage oscilloscope, which allows us to perform various types of analysis as all the signal pulses constituting TOF SI mass spectra can be recorded digitally in the system. Effects of the SI counting strategy on SI mass spectra were investigated for C{sub 8} and C{sub 60} cluster ion impacts on an organically contaminated silicon wafer and on polytetrafluoroethylene targets by comparing TOF SI mass spectra obtained from the same recorded signals with different SI counting procedures. Our results show that the use of a counting system, which can cope with high SI yields, is necessary for quantitative analysis of SI mass spectra obtained under high SI yield per impact conditions, including the case of cluster ion impacts on organic compounds.

  13. Method for determination of acephate, methamidophos, omethoate, dimethoate, ethylenethiourea and propylenethiourea in human urine using high-performance liquid chromatography-atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

    Montesano, M Angela; Olsson, Anders O; Kuklenyik, Peter; Needham, Larry L; Bradman, A S A; Barr, Dana B

    2007-07-01

    Because of increasing concern about widespread use of insecticides and fungicides, we have developed a highly sensitive analytical method to quantify urine-specific urinary biomarkers of the organophosphorus pesticides acephate, methamidophos, omethoate, dimethoate, and two metabolites from the fungicides alkylenebis-(dithiocarbamate) family: ethylenethiourea and propylenethiourea. The general sample preparation included lyophilization of the urine samples followed by extraction with dichloromethane. The analytical separation was performed by high-performance liquid chromatography (HPLC), and detection by a triple quadrupole mass spectrometer with and atmospheric pressure chemical ionization source in positive ion mode using multiple reaction monitoring and tandem mass spectrometry (MS/MS) analysis. Two different Thermo-Finnigan (San Jose, CA, USA) triple quadrupole mass spectrometers, a TSQ 7,000 and a TSQ Quantum Ultra, were used in these analyses; results are presented comparing the method specifications of these two instruments. Isotopically labeled internal standards were used for three of the analytes. The use of labeled internal standards in combination with HPLC-MS/MS provided a high degree of selectivity and precision. Repeated analysis of urine samples spiked with high, medium and low concentration of the analytes gave relative standard deviations of less than 18%. For all compounds the extraction efficiency ranged between 52% and 63%, relative recoveries were about 100%, and the limits of detection were in the range of 0.001-0.282 ng/ml. PMID:17440487

  14. Simultaneous airborne nitric acid and formic acid measurements using a chemical ionization mass spectrometer around the UK: Analysis of primary and secondary production pathways

    NASA Astrophysics Data System (ADS)

    Le Breton, Michael; Bacak, Asan; Muller, Jennifer B. A.; Xiao, Ping; Shallcross, Beth M. A.; Batt, Rory; Cooke, Michael C.; Shallcross, Dudley E.; Bauguitte, S. J.-B.; Percival, Carl J.

    2014-02-01

    The first simultaneous measurements of formic and nitric acid mixing ratios around the United Kingdom were measured on the FAAM BAe-146 research aircraft with a chemical ionization mass spectrometer using I- reagent ions at 0.8 Hz. Analysis of the whole dataset shows that formic acid and nitric acid are positively correlated as illustrated by other studies (e.g. Veres et al., 2011). However, initial evidence indicates a prominent direct source of formic acid and also a significant source when O3 levels are high, suggesting the importance of the ozonolysis of 1-alkenes. A trajectory model was able to reproduce the formic acid concentrations by both the inclusion of a primary vehicle source and production via ozonolysis of propene equivalent 1-alkene levels. Inspection of data archives implies these levels of 1-alkene are possible after 11 am, but formic acid and nitric acid plumes early in the flight are too high for the model to replicate. These data show the relationship between nitric acid and formic acid cannot solely be attributed to related photochemical production. The simultaneous measurement of HCOOH and HNO3 has been implemented to estimate OH levels along the flight track assuming a relationship between formic and nitric acid in photochemical plumes and a constant source of 1-alkene.

  15. Chemical separation and mass spectrometry of Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial materials using thermal ionization mass spectrometry.

    PubMed

    Yamakawa, Akane; Yamashita, Katsuyuki; Makishima, Akio; Nakamura, Eizo

    2009-12-01

    A sequential chemical separation technique for Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial silicate rocks was developed for precise and accurate determination of elemental concentration by the isotope dilution method (ID). The technique uses a combination of cation-anion exchange chromatography and Eichrom nickel specific resin. The method was tested using a variety of matrixes including bulk meteorite (Allende), terrestrial peridotite (JP-1), and basalt (JB-1b). Concentrations of each element was determined by thermal ionization mass spectrometry (TIMS) using W filaments and a Si-B-Al type activator for Cr, Fe, Ni, and Zn and a Re filament and silicic acid-H3PO4 activator for Cu. The method can be used to precisely determine the concentrations of these elements in very small silicate samples, including meteorites, geochemical reference samples, and mineral standards for microprobe analysis. Furthermore, the Cr mass spectrometry procedure developed in this study can be extended to determine the isotopic ratios of 53Cr/52Cr and 54Cr/52Cr with precision of approximately 0.05epsilon and approximately 0.10epsilon (1epsilon = 0.01%), respectively, enabling cosmochemical applications such as high precision Mn-Cr chronology and investigation of nucleosynthetic isotopic anomalies in meteorites. PMID:19886654

  16. A method for simultaneous analysis of phytosterols and phytosterol esters in tobacco leaves using non aqueous reversed phase chromatography and atmospheric pressure chemical ionization mass spectrometry detector.

    PubMed

    Ishida, Naoyuki

    2014-05-01

    While numerous analytical methods for phytosterols have been reported, the similar polarity and large molecules of phytosterol esters have made the methods lengthy and complicated. For this reason, an analytical method that could completely separate phytosterol esters including the higher fatty acids such as palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid in addition to phytosterols without preliminary separation was developed. The separation was accomplished by non-aqueous reversed phase chromatography technique using only acetone and acetonitrile. An atmospheric pressure chemical ionization/mass spectrometry detector configured at selected ion monitoring mode was hyphenated with the separation system to detect phytosterols and phytosterol esters. Twenty-four types of these were consequently separated and then identified with their authentic components. The calibration curve was drawn in the range of about 5 to 25,000 ng/mL with a regression coefficient over 0.999. The limit of detection and limit of quantification, respectively, ranged from 0.9 to 3.0 ng/mL and from 3.0 to 11.0 ng/mL. Recovery rates ranged from 80 to 120%. The quantification results were subjected to statistical analysis and hierarchical clustering analysis, and were used to determine the differences in the amounts of phytosterols and phytosterol esters across tobacco leaves. The newly developed method succeeded in clarifying the whole composition of phytosterols and phytosterol esters in tobacco leaves and in explaining compositional differences across the variety of tobacco leaves. PMID:24690307

  17. Analysis of 1,2-diol diesters in vernix caseosa by high-performance liquid chromatography - atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Šub?íková, Lenka; Hoskovec, Michal; Vrkoslav, Vladimír; ?melíková, Tereza; Háková, Eva; Míková, Radka; Coufal, Pavel; Doležal, Antonín; Plavka, Richard; Cva?ka, Josef

    2015-01-23

    Fatty acid diesters of long-chain 1,2-diols (1,2-DDE), or type II wax diesters, were analyzed in the vernix caseosa of a newborn girl. 1,2-DDE were isolated from the total lipid extract by the semipreparative TLC using plates coated with silica gel. Chromatographic separation of the 1,2-DDE molecular species was achieved on the non-aqueous reversed-phase HPLC with two Nova-Pak C18 columns connected in series (a total length of 45cm) and using an acetonitrile-ethyl acetate gradient. 1,2-DDE eluted from the column in the order of their equivalent chain number. The analytes were detected as ammonium adducts by an ion-trap mass spectrometer equipped with an atmospheric pressure chemical ionization source. Their structures were elucidated using tandem mass spectrometry with MS, MS(2) and MS(3) steps in a data-dependent mode. More than two thousand molecular species of 1,2-DDE were identified in 141 chromatographic peaks. The most abundant 1,2-DDE were monounsaturated lipids consisting of a C22 diol and a C18:1 fatty acid together with C16:0, C14:0 or C15:0 fatty acids. The positions of double bonds were characterized by the fragmentation of [M+C3H5N](+) formed in the ion source. PMID:25555408

  18. [Determination of aliphatic amines by high performance liquid chromatography with fluorescence and atmospheric pressure chemical ionization detection and identification by mass spectrometry].

    PubMed

    Chen, Xiangming; Shi, Yunwei; Zhao, Xian'en; Zhang, Haifeng; You, Jinmao

    2005-11-01

    Aliphatic amines exist widely in nature. Therefore, quick and precise determination of aliphatic amines is of great significance. A simple and highly sensitive method based on the derivatization of aliphatic amines utilizing 1,2-benzo-3,4-dihydrocarbazole-9-acetic acid (BCAA) as the novel pre-column derivatization reagent followed by high performance liquid chromatography with fluorescence detection and online mass spectrometric identification was developed. Optimum derivatization was obtained by the reaction of aliphatic amines with BCAA at 50 degrees C for 15 min in the presence of 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDAC) in acetonitrile solvent. The condition of derivatization was mild and the yield of derivative each aliphatic amine was higher than 94%. Derivatives were sufficiently stable to be efficiently analyzed by high performance chromatography without pretreatment. On a reversed-phase BDS-C18 column, twelve aliphatic amine derivatives (C8 - C12) were separated under gradient elution with baseline resolution. The precise determining aliphatic amines from soil and wastewater samples was obtained by post-column online mass spectrometric identification with atmospheric pressure chemical ionization (APIC) source under positive mode detection. The established method exhibited excellent reproducibility and recovery. Linear responses were observed with coefficients over 0.999 3. The detection limits (at signal-to-noise ratio of 3: 1) were 12 - 28 fmol. PMID:16498997

  19. GC/MS-positive ion chemical ionization and MS/MS study of volatile benzene compounds in five different woods used in barrel making.

    PubMed

    Flamini, Riccardo; Dalla Vedova, Antonio; Cancian, Davide; Panighel, Annarita; De Rosso, Mirko

    2007-05-01

    Extracts from acacia, chestnut, cherry, mulberry, and oak wood, used in making barrels for aging wine and spirits were studied by GC/MS positive ion chemical ionization (PICI). Wood chips were extracted by a 50% water/ethanol solution and a tartrate buffer pH 3.2-12% ethanol (model wine) solution. The principal compounds identified in extracts were guaiacol-containing aldehydes and alcohols, such as benzaldehyde and derivatives, vanillin and syringaldehyde, cinnamaldehyde and coniferaldehyde, eugenol and methoxyeugenol, guaiacol and methoxyguaiacol derivatives. PICI using methane as reagent gas produced a high yield of the protonated molecular ion of volatile phenols, compound identification was confirmed by collision-induced-dissociation (CID) experiments on [M + H](+) species. MS/MS fragmentation patterns were studied with standard compounds: guaiacol-containing molecules were characterized by neutral methyl and methanol losses, benzaldehyde derivatives by CO loss. Acacia wood extracts contained significant syringaldehyde and anisaldehyde, but no eugenol and methoxyeugenol. Significant syringaldehyde, eugenol and methoxyeugenol, and high vanillin were found in chestnut and oak wood extracts; low presence of volatile benzene compounds was found in mulberry wood extracts. Cherry wood extracts were characterized by the presence of several benzaldehyde derivatives and high trimethoxyphenol. PMID:17370248

  20. Carbamazepine in municipal wastewater and wastewater sludge: ultrafast quantification by laser diode thermal desorption-atmospheric pressure chemical ionization coupled with tandem mass spectrometry.

    PubMed

    Mohapatra, D P; Brar, S K; Tyagi, R D; Picard, P; Surampalli, R Y

    2012-09-15

    In this study, the distribution of the anti-epileptic drug carbamazepine (CBZ) in wastewater (WW) and aqueous and solid phases of wastewater sludge (WWS) was carried out. A rapid and reliable method enabling high-throughput sample analysis for quicker data generation, detection, and monitoring of CBZ in WW and WWS was developed and validated. The ultrafast method (15s per sample) is based on the laser diode thermal desorption-atmospheric pressure chemical ionization (LDTD-APCI) coupled to tandem mass spectrometry (MS/MS). The optimization of instrumental parameters and method application for environmental analysis are presented. The performance of the novel method was evaluated by estimation of extraction recovery, linearity, precision and detection limit. The method detection limits was 12 ng L(-1) in WW and 3.4 ng g(-1) in WWS. The intra- and inter-day precisions were 8% and 11% in WW and 6% and 9% in WWS, respectively. Furthermore, three extraction methods, ultrasonic extraction (USE), microwave-assisted extraction (MAE) and accelerated solvent extraction (ASE) with three different solvent condition such as methanol, acetone and acetonitrile:ethyle acetate (5:1, v/v) were compared on the basis of procedural blank and method recovery. Overall, ASE showed the best extraction efficiency with methanol as compared to USE and MAE. Furthermore, the quantification of CBZ in WW and WWS samples showed the presence of contaminant in all stages of the treatment plant. PMID:22967548

  1. 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

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

    PubMed Central

    Raina, Renata; Etter, Michele L.

    2010-01-01

    A new liquid chromatography (LC)-negative ion electrospray ionization (ESI?)–tandem mass spectrometry (MS/MS) method with post-column addition of ammonia in methanol has been developed for the analysis of acid herbicides: 2,4-dichlorophenoxy acetic acid, 4-chloro-o-tolyloxyacetic acid, 2-(2-methyl-4-chlorophenoxy)butyric acid, mecoprop, dichlorprop, 4-(2,4-dichlorophenoxy) butyric acid, 2,4,5-trichlorophenoxy propionic acid, dicamba and bromoxynil, along with their degradation products: 4-chloro-2-methylphenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and 3,5-dibromo-4-hydroxybenzoic acid. The samples were extracted from the surface water matrix using solid-phase extraction (SPE) with a polymeric sorbent and analyzed with LC ESI? with selected reaction monitoring (SRM) using a three-point confirmation approach. Chromatography was performed on a Zorbax Eclipse XDB-C18 (50 × 4.6 mm i.d., 1.8 ?m) with a gradient elution using water-methanol with 2 mM ammonium acetate mobile phase at a flow rate of 0.15 mL/min. Ammonia in methanol (0.8 M) was added post-column at a flow rate of 0.05 mL/min to enhance ionization of the degradation products in the MS source. One SRM transition was used for quantitative analysis while the second SRM along with the ratio of SRM1/SRM2 within the relative standard deviation determined by standards for each individual pesticide and retention time match were used for confirmation. The standard deviation of ratio of SRM1/SRM2 obtained from standards run on the day of analysis for different phenoxyacid herbicides ranged from 3.9 to 18.5%. Limits of detection (LOD) were between 1 and 15 ng L?1 and method detection limits (MDL) with strict criteria requiring <25% deviation of peak area from best-fit line for both SRM1 and SRM2 ranged from 5 to 10 ng L?1 for acid ingredients (except dicamba at 30 ng L?1) and from 2 to 30 ng L?1 for degradation products. The SPE-LC-ESI? MS/MS method permitted low nanogram-per-liter determination of pesticides and degradation products for surface water samples. PMID:20212919

  3. 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.

    2014-11-19

    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.

  4. 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...

  5. 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.

  6. Heat stress evaluation of two-layer chemical demilitarization ensembles with a full face negative pressure respirator.

    PubMed

    Fletcher, Oclla Michele; Guerrina, Ryan; Ashley, Candi D; Bernard, Thomas E

    2014-01-01

    The purpose of this study was to examine the heat stress effects of three protective clothing ensembles: (1) protective apron over cloth coveralls including full face negative pressure respirator (APRON); (2) the apron over cloth coveralls with respirator plus protective pants (APRON+PANTS); and (3) protective coveralls over cloth coveralls with respirator (PROTECTIVE COVERALLS). In addition, there was a no-respirator ensemble (PROTECTIVE COVERALLS-noR), and WORK CLOTHES as a reference ensemble. Four acclimatized male participants completed a full set of five trials, and two of the participants repeated the full set. The progressive heat stress protocol was used to find the critical WBGT (WBGTcrit) and apparent total evaporative resistance (Re,T,a) at the upper limit of thermal equilibrium. The results (WBGTcrit [°C-WBGT] and Re,T,a [kPa?m(2) W(-1)]) were WORK CLOTHES (35.5, 0.0115), APRON (31.6, 0.0179), APRON+PANTS (27.7, 0.0244), PROTECTIVE COVERALLS (25.9, 0.0290), and PROTECTIVE COVERALLS-noR (26.2, 0.0296). There were significant differences among the ensembles. Supporting previous studies, there was little evidence to suggest that the respirator contributed to heat stress. PMID:24705801

  7. Heat Stress Evaluation of Two-layer Chemical Demilitarization Ensembles with a Full Face Negative Pressure Respirator

    PubMed Central

    FLETCHER, Oclla Michele; GUERRINA, Ryan; ASHLEY, Candi D.; BERNARD, Thomas E.

    2014-01-01

    The purpose of this study was to examine the heat stress effects of three protective clothing ensembles: (1) protective apron over cloth coveralls including full face negative pressure respirator (APRON); (2) the apron over cloth coveralls with respirator plus protective pants (APRON+PANTS); and (3) protective coveralls over cloth coveralls with respirator (PROTECTIVE COVERALLS). In addition, there was a no-respirator ensemble (PROTECTIVE COVERALLS-noR), and WORK CLOTHES as a reference ensemble. Four acclimatized male participants completed a full set of five trials, and two of the participants repeated the full set. The progressive heat stress protocol was used to find the critical WBGT (WBGTcrit) and apparent total evaporative resistance (Re,T,a) at the upper limit of thermal equilibrium. The results (WBGTcrit [°C-WBGT] and Re,T,a [kPa?m2 W?1]) were WORK CLOTHES (35.5, 0.0115), APRON (31.6, 0.0179), APRON+PANTS (27.7, 0.0244), PROTECTIVE COVERALLS (25.9, 0.0290), and PROTECTIVE COVERALLS-noR (26.2, 0.0296). There were significant differences among the ensembles. Supporting previous studies, there was little evidence to suggest that the respirator contributed to heat stress. PMID:24705801

  8. 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

  9. Evaluation of the Bruker Biotyper and Vitek MS Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry Systems for Identification of Nonfermenting Gram-Negative Bacilli Isolated from Cultures from Cystic Fibrosis Patients

    PubMed Central

    Marko, Daniel C.; Saffert, Ryan T.; Cunningham, Scott A.; Hyman, Jay; Walsh, John; Arbefeville, Sophie; Howard, Wanita; Pruessner, Jon; Safwat, Nedal; Cockerill, Franklin R.; Bossler, Aaron D.; Patel, Robin

    2012-01-01

    The Bruker Biotyper and Vitek MS matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry (MS) instruments were evaluated for the identification of nonfermenting Gram-negative bacilli (NFGNB) by a blinded comparison to conventional biochemical or molecular methods. Two hundred NFGNB that were recovered from cultures from cystic fibrosis patients in the University of Iowa Health Care (UIHC) Microbiology Laboratory between 1 January 2006 and 31 October 2010 were sent to Mayo Clinic for analysis with the Bruker Biotyper (software version 3.0) and to bioMérieux for testing with Vitek MS (SARAMIS database version 3.62). If two attempts at direct colony testing failed to provide an acceptable MALDI-TOF identification, an extraction procedure was performed. The MS identifications from both of these systems were provided to UIHC for comparison to the biochemical or molecular identification that had been reported in the patient record. Isolates with discordant results were analyzed by 16S rRNA gene sequencing at UIHC. After discrepancy testing, the Bruker Biotyper result agreed with the biochemical or molecular method, with 72.5% of isolates to the species level, 5.5% to the complex level, and 19% to the genus level (3% not identified). The level of agreement for Vitek MS was 80% species, 3.5% complex, 6% genus, and 3.5% family (7% not identified). Both MS systems provided rapid (?3 min per isolate) and reliable identifications. The agreement of combined species/complex/genus-level identification with the reference method was higher for the Bruker Biotyper (97% versus 89.5%, P = 0.004) but required an extraction step more often. Species-level agreement with the reference method was similar for both MS systems (72.5% and 80%, P = 0.099). PMID:22495566

  10. Analysis of ketamine and norketamine in urine by automatic solid-phase extraction (SPE) and positive ion chemical ionization–gas chromatography–mass spectrometry (PCI–GC–MS)

    Microsoft Academic Search

    Eun-mi Kim; Ju-seon Lee; Sang-kil Choi; Mi-ae Lim; Hee-sun Chung

    2008-01-01

    Ketamine (KT) is widely abused for hallucination and also misused as a “date-rape” drug in recent years. An analytical method using positive ion chemical ionization–gas chromatography–mass spectrometry (PCI–GC–MS) with an automatic solid-phase extraction (SPE) apparatus was studied for the determination of KT and its major metabolite, norketamine (NK), in urine. Six ketamine suspected urine samples were provided by the police.

  11. 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

    Microsoft Academic Search

    Ramin Amini; Ahmad Rouhollahi; Mina Adibi; Ali Mehdinia

    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

  12. Characterization of triglycerides in vegetable oils by silver-ion packed-column supercritical fluid chromatography coupled to mass spectroscopy with atmospheric pressure chemical ionization and coordination ion spray

    Microsoft Academic Search

    P. Sandra; A. Medvedovici; Y. Zhao; F. David

    2002-01-01

    Characterization of triglycerides in vegetable oils was achieved by silver-ion packed-column supercritical fluid chromatography (SI-pSFC) with mass spectrometric detection. Hyphenation was made using commercially available liquid chromatography–mass spectrometry (LC–MS) interfaces without any modification. A make-up fluid was delivered through a T-piece placed before or after the SFC restrictor by means of a high pressure pump. Atmospheric pressure chemical ionization (APCI)

  13. Shock tube study of ionization rates of NaCl-contaminated argon

    NASA Technical Reports Server (NTRS)

    Schneider, K.-P.; Park, C.

    1975-01-01

    Electron density, electron temperature, and concentration of excited sodium atoms are measured in the weakly ionized regime behind a shock wave in impure argon in a shock tube using microwave techniques and spectrally resolved radiometry. Evidence is presented to show that an apparent increase in the rate of ionization is due to electron detachment of negative chlorine ions produced from sodium chloride vapor contained as an impurity. To be consistent with this chemical model, rate coefficients are found in the temperature range between 5500 and 8600 K for the dissociation of NaCl into an ion pair, dissociation of NaCl into a neutral pair, and electron detachment of a negative chlorine ion. Electron temperature is lower than heavy-particle temperature by roughly 1000 K. The electron-argon impact-ionization rate coefficient is a weak function of electron temperature in contradiction to expectation.

  14. The influence of the electrolyte on chemical and morphological modifications of an iron sulfide thin film negative electrode.

    PubMed

    Liao, Feng; ?wiatowska, Jolanta; Maurice, Vincent; Seyeux, Antoine; Klein, Lorena H; Zanna, Sandrine; Marcus, Philippe

    2015-01-01

    The chemical and morphological modifications of FeS thin film as anode material for LiBs have been studied in detail in two classical electrolytes usually used in Li-ion batteries: 1 M LiClO4-PC and 1 M LiPF6-EC/DMC. The X-ray photoelectron spectroscopic (XPS) analysis evidenced the formation of a solid electrolyte interphase (SEI) that contains a more significant amount of inorganic salt residues formed in LiPF6-EC/DMC than in LiClO4-PC, which is likely to increase the ionic resistivity of the SEI, thus impeding the lithiation-delithiation in the first cycles while improving its reversibility. Ion depth profiles performed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) show volume expansion-shrinkage of the thin film leading to cracking and pulverization of the electrode material, which is also confirmed by scanning electron microscopy (SEM) analysis. The prolonged cycling results in penetration and accumulation of the electrolyte in a bulk electrode with accumulation of the inorganic species in the inner part of the SEI enhanced in a fluoride-containing electrolyte. Cycling in these two different electrolytes leads also to formation of two different electrode morphologies: with a compact electrode structure formed in LiClO4-PC and a foam-like, porous structure in LiPF6-EC/DMC. A model of this conversion-type thin film electrode modification based on these thorough spectroscopic and microscopic analyses induced by cycling in two different electrolytes is proposed. PMID:25407398

  15. Chemistry of ?-pinene and naphthalene oxidation products generated in a Potential Aerosol Mass (PAM) chamber as measured by acetate chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chhabra, P. S.; Lambe, A. T.; Canagaratna, M. R.; Stark, H.; Jayne, J. T.; Onasch, T. B.; Davidovits, P.; Kimmel, J. R.; Worsnop, D. R.

    2014-07-01

    Recent developments in high resolution, time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) have made possible the direct detection of atmospheric organic compounds in real-time with high sensitivity and with little or no fragmentation, including low volatility, highly oxygenated organic vapors that are precursors to secondary organic aerosol formation. Here, for the first time, we examine gas-phase O3 and OH oxidation products of ?-pinene and naphthalene formed in the PAM flow reactor with an HR-ToF-CIMS using acetate reagent ion chemistry. Integrated OH exposures ranged from 1.2 × 1011 to 9.7 × 1011 molec cm-3 s, corresponding to approximately 1.0 to 7.5 days of equivalent atmospheric oxidation. Measured gas-phase organic acids are similar to those previously observed in environmental chamber studies. For both precursors, we find that acetate-CIMS spectra capture both functionalization (oxygen addition) and fragmentation (carbon loss) as a function of OH exposure. The level of fragmentation is observed to increase with increased oxidation. We present a method that estimates vapor pressures of organic molecules using the measured O/C ratio, H/C ratio, and carbon number for each compound detected by the CIMS. The predicted condensed-phase SOA average acid yields and O/C and H/C ratios agree within uncertainties with previous AMS measurements and ambient CIMS results. While acetate reagent ion chemistry is used to selectively measure organic acids, in principle this method can be applied to additional reagent ion chemistries depending on the application.

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

    PubMed

    Cherlet, M; De Baere, S; Croubels, S; De Backer, P

    2000-06-01

    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 samples. Methyllevamisole was used as the internal standard. Chromatographic separation was achieved on a LiChrospher 60 RP-select B (5 microm) column using a mixture of 0.1 M ammonium acetate in water and acetonitrile as the mobile phase. The mass spectrometer was operated in MS-MS full scanning mode. The method was validated for the analysis of various porcine tissues: muscle, kidney, liver, fat and skin plus fat, according to the requirements defined by the European Community. Calibration graphs were prepared for all tissues and good linearity was achieved over the concentration ranges tested (r>0.99 and goodness of fit <10%). Limits of quantification of 5.0 ng/g were obtained for the analysis of levamisole in muscle, kidney, fat and skin plus fat tissues, and of 50.0 ng/g for liver analysis, which correspond in all cases to half the MRLs (maximum residue limits). Limits of detection ranged between 2 and 4 ng/g tissue. The within-day and between-day precisions (RSD, %) and the results for accuracy fell within the ranges specified. The method has been successfully used for the quantitative determination of levamisole in tissue samples from pigs medicated via drinking water. Moreover the product ion spectra of the levamisole peak in spiked and incurred tissue samples were in close agreement (based on ion ratio measurements) with those of standard solutions, indicating the worthiness of the described method for pure qualitative purposes. PMID:10901133

  17. Aqueous-phase photooxidation of levoglucosan - a mechanistic study using aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS)

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Mungall, E. L.; Lee, A. K. Y.; Aljawhary, D.; Abbatt, J. P. D.

    2014-09-01

    Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (-2H) were observed among the products detected, providing useful information for determining potential reaction mechanisms and sequences. Additionally, bond-scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double-bond-equivalence-to-carbon ratio (DBE/#C). The trajectory of LG photooxidation on this plot suggests formation of polycarbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M-1 s-1. By coupling an aerosol mass spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol ToF-CIMS. The trajectory of LG photooxidation on a f44-f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the ambient atmosphere.

  18. Aqueous-phase photooxidation of levoglucosan - a mechanistic study using Aerosol Time of Flight Chemical Ionization Mass Spectrometry (Aerosol-ToF-CIMS)

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Mungall, E. L.; Lee, A. K. Y.; Aljawhary, D.; Abbatt, J. P. D.

    2014-04-01

    Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase, despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by Aerosol Time of Flight Chemical Ionization Mass Spectrometry (Aerosol-ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol-ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (-2H) were observed among the products detected, providing useful information to determine potential reaction mechanisms and sequences. As well, bond scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double bond equivalence to carbon ratio (DBE / #C). The trajectory of LG photooxidation on this plot suggests formation of poly-carbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M-1 s-1. By coupling an Aerosol Mass Spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol-ToF-CIMS. The trajectory of LG photooxidation on a f44-f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the ambient atmosphere.

  19. 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

  20. 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

  1. The Modulation of Endoplasmic Reticulum Stress by Chemical Chaperone Upregulates Immune Negative Cytokine IL-35 in Apolipoprotein E-Deficient Mice

    PubMed Central

    Wang, Bo; Dai, Shen; Dong, Zhaojing; Sun, Yue; Song, Xingguo; Guo, Chun; Zhu, Faliang; Wang, Qun; Zhang, Lining

    2014-01-01

    Interleukin (IL)-35 is a newly identified immune negative molecule which is secreted by CD4+Foxp3+ T regulatory cells (Tregs) and contributes to their suppressive capacity. Early data have shown that IL-35 inhibits development of several autoimmune diseases. However, the role of IL-35 in atherosclerosis, a lipid-driven chronic inflammatory disease in arterial wall, remains to be investigated. Here, we found that IL-35 was involved in atherosclerosis in apolipoprotein E-deficient (ApoE?/?) mice. ApoE?/? mice with established atherosclerotic lesion displayed a lower level of IL-35 compared to age-matched wild type C57BL/6 mice without plaque. However, IL-35 expression increased significantly in ApoE?/? mice with attenuated plaque. More importantly, we found that modulation of ER stress treated by chemical chaperone, 4-Phenyl butyric acid (PBA) in vivo, mainly upregulated immune negative regulating molecule IL-35, as well as IL-10 and Foxp3, accompanied by increased Tregs. However, no obvious impact on pro-inflammatory molecules such as TNF-?, IFN-?, IL-17 and IL-23 was observed, which provides new insight into the benefit of ER stress recovery from attenuated plaque. Our results suggest that IL-35 might have a potential value for atherosclerotic therapy. PMID:24498194

  2. 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.

  3. A high efficiency, kinetic-ejection negative ion source for RIB generation

    SciTech Connect

    Alton, G.D.; Liu, Y.; Williams, C.; Murray, S.N. (Physics Division, Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, Tennessee 37831-6368 (United States))

    1999-04-01

    Chemically active radioactive species, diffused from RIB target materials, often arrive at the ionization chamber of the source in a variety of molecular forms. Because of the low probability for simultaneously dissociating and efficiently ionizing the individual atomic constituents of molecules with conventional hot-cathode electron-impact ion sources, the species of interest are often distributed in several mass channels in the form of molecular side-band beams and consequently, their intensities are diluted. The sputter negative ion beam generation technique offers an efficient means for simultaneously dissociating and ionizing highly electronegative atomic species present in molecular carriers. We have incorporated these principles in the design and fabrication of a kinetic ejection negative ion source and evaluated its potential for generating [sup 17,18]F[sup [minus

  4. Peroxynitric acid (HO2NO2) measurements during the UBWOS 2013 and 2014 studies using iodide ion chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Veres, P. R.; Roberts, J. M.; Wild, R. J.; Edwards, P. M.; Brown, S. S.; Bates, T. S.; Quinn, P. K.; Johnson, J. E.; Zamora, R. J.; de Gouw, J.

    2015-02-01

    Laboratory work is reported here establishing iodide ion chemical ionization mass spectrometry (I- CIMS) as a sensitive method for the unambiguous detection of peroxynitric acid (HO2NO2, PNA). A~dynamic calibration source for HO2NO2, HO2, and HONO was developed and calibrated using a~novel total NOy detector (NOy CaRDS). Photochemical sources of these species were used for the calibration and validation of the I- CIMS instrument for detection of HO2NO2. A dual inlet system was developed to determine differences in the instrument response when using a heated inlet dissociator (150 °C) and a "cold" room-temperature inlet. HO2NO2 was detected as I-HO2- (m/z 160), NO3- (m/z 62) and I-HO2NO2- (m/z 206). The I- CIMS normalized sensitivity to peroxynitric acid was 2.0 Hz pptv-1 with a detection limit (3?) of 40 pptv via detection of the I-HO2- (m/z 160) cluster ion using an inlet dissociator at a temperature of 150 °C. Alternatively, PNA was detected via I- CIMS with a cold inlet at both the NO3- (m/z 62) and I-HO2NO2- (m/z 206) ions with normalized detection sensitivities of 144 and 0.4 Hz pptv-1 respectively. The cold inlet sensitivity of iodide CIMS towards the detection of HO2 radicals, also via detection at the I-HO2- cluster ion, a potential HO2NO2 interference, was approximately 2.6 Hz pptv-1 with an instrumental detection limit (3?) of 20 pptv. Ambient observations of HO2NO2 using I- CIMS were made during the 2013 and 2014 Uintah Basin Wintertime Ozone Study (UBWOS) are presented. Strong inversions leading to a build-up of many primary and secondary pollutants as well as low temperatures drove daytime HO2NO2 as high as 1.5 ppbv during the 2013 study. A comparison of HO2NO2 observations to mixing ratios predicted using a chemical box model describing an ozone formation event observed during the 2013 wintertime shows agreement in the daily maxima HO2NO2 mixing ratio, but a significant difference os several hours in the timing of the observed maxima. Observations of vertical gradients suggest that the ground snow surface potentially serves as both a net sink and source of HO2NO2 depending on time of day. Sensitivity tests using a chemical box model indicate that the lifetime of HO2NO2 with respect to deposition has a non-negligible impact on ozone production rates on the order of 10%.

  5. 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

  6. Screening and quantification of pesticide residues in fruits and vegetables making use of gas chromatography-quadrupole time-of-flight mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Cervera, M I; Portolés, T; López, F J; Beltrán, J; Hernández, F

    2014-11-01

    An atmospheric pressure chemical ionization source has been used to enhance the potential of gas chromatography coupled with quadrupole time-of-flight (QTOF) mass spectrometry (MS) for screening and quantification purposes in pesticide residue analysis. A screening method developed in our laboratory for around 130 pesticides has been applied to fruit and vegetable samples, including strawberries, oranges, apples, carrots, lettuces, courgettes, red peppers, and tomatoes. Samples were analyzed together with quality control samples (at 0.05 mg/kg) for each matrix and for matrix-matched calibration standards. The screening strategy consisted in first rapid searching and detection, and then a refined identification step using the QTOF capabilities (MS(E) and accurate mass). Identification was based on the presence of one characteristic m/z ion (Q) obtained with the low collision energy function and at least one fragment ion (q) obtained with the high collision energy function, both with mass errors of less than 5 ppm, and an ion intensity ratio (q/Q) within the tolerances permitted. Following this strategy, 15 of 130 pesticides were identified in the samples. Afterwards, the quantitation capabilities were tested by performing a quantitative validation for those pesticides detected in the samples. To this aim, five matrices were selected (orange, apple, tomato, lettuce, and carrot) and spiked at two concentrations (0.01 and 0.1 mg/kg), and quantification was done using matrix-matched calibration standards (relative responses versus triphenyl phosphate used as an internal standard). Acceptable average recoveries and relative standard deviations were obtained for many but not all pesticide-matrix combinations. These figures allowed us to perform a retrospective quantification of positives found in the screening without the need for additional analysis. Taking advantage of the accurate-mass full-spectrum data provided by QTOF MS, we searched for a higher number of compounds (up to 416 pesticides) in a second stage by performing extra data processing without any new sample injection. Several more pesticides were detected, confirmed, and/or tentatively identified when the reference standard was unavailable, illustrating in this way the potential of gas chromatography-QTOF MS to detect pesticides in addition to the ones targeted in quantitative analysis of pesticides in food matrices. PMID:24828980

  7. 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

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

    PubMed

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

    2013-11-01

    In this work, the mass spectrometry behaviour of the veterinary drug family of phenicols, including chloramphenicol (CAP) and its related compounds thiamphenicol (TAP), florfenicol (FF) and FF amine (FFA), was studied. Several atmospheric pressure ionization sources, electrospray (ESI), atmospheric pressure chemical ionization and atmospheric pressure photoionization were compared. In all atmospheric pressure ionization sources, CAP, TAP and FF were ionized in both positive and negative modes; while for the metabolite FFA, only positive ionization was possible. In general, in positive mode, [M + H](+) dominated the mass spectrum for FFA, while the other compounds, CAP, TAP and FF, with lower proton affinity showed intense adducts with species present in the mobile phase. In negative mode, ESI and atmospheric pressure photoionization showed the deprotonated molecule [M-H](-), while atmospheric pressure chemical ionization provided the radical molecular ion by electron capture. All these ions were characterized by tandem mass spectrometry using the combined information obtained by multistage mass spectrometry and high-resolution mass spectrometry in a quadrupole-Orbitrap instrument. In general, the fragmentation occurred via cyclization and losses or fragmentation of the N-(alkyl)acetamide group, and common fragmentation pathways were established for this family of compounds. A new chemical structure for the product ion at m/z 257 for CAP, on the basis of the MS(3) and MS(4) spectra is proposed. Thermally assisted ESI and selected reaction monitoring are proposed for the determination of these compounds by ultra high-performance liquid chromatography coupled to tandem mass spectrometry, achieving instrumental detection limits down to 0.1 pg. PMID:24259213

  9. Simple and sensitive method for determination of nitrated polycyclic aromatic hydrocarbons in diesel exhaust particles by gas chromatography-negative ion chemical ionisation tandem mass spectrometry.

    PubMed

    Kawanaka, Youhei; Sakamoto, Kazuhiko; Wang, Ning; Yun, Sun-Ja

    2007-09-01

    An extremely simple and sensitive method was developed for determination of nitrated polycyclic aromatic hydrocarbons (nitro-PAHs; mono-nitro-PAHs and dinitropyrenes) in diesel exhaust particles (DEPs) by gas chromatography-negative ion chemical ionisation tandem mass spectrometry (GC/NCI/MS/MS). We used two types of column in GC/NCI/MS/MS analysis. A polar column was used for determination of mono-nitro-PAHs, and a non-polar column was used for determination of dinitropyrenes and mono-nitro-PAHs except nitrofluoranthenes. The proposed method requires no clean-up procedure. The limits of detection ranged from 0.01 to 0.09 pg for all compounds tested. The applicability of the method to DEP samples was validated using diesel particulate standard reference materials (SRMs). Although DEPs contain complex matrices, all compounds could be detected easily in SRM2975 (diesel particulate matter) and SRM1975 (diesel particulate extract) without a clean-up procedure. The RSDs were less than 5% for all compounds examined. The quantitative results for SRMs exhibited good agreement with the available data in the literature. These results indicate that the proposed GC/NCI/MS/MS method is useful for determination of nitro-PAHs in DEP samples. PMID:17619018

  10. Three chamber negative ion source

    DOEpatents

    Leung, K.N.; Ehlers, K.W.; Hiskes, J.R.

    1983-11-10

    It is an object of this invention provide a negative ion source which efficiently provides a large flux of negatively ionized particles. This invention provides a volume source of negative ions which has a current density sufficient for magnetic fusion applications and has electrons suppressed from the output. It is still another object of this invention to provide a volume source of negative ions which can be electrostatically accelerated to high energies and subsequently neutralized to form a high energy neutral beam for use with a magnetically confined plasma.

  11. Negative mass

    NASA Astrophysics Data System (ADS)

    Hammond, Richard T.

    2015-03-01

    Some physical aspects of negative mass are examined. Several unusual properties, such as the ability of negative mass to penetrate any armor, are analysed. Other surprising effects include the bizarre system of negative mass chasing positive mass, naked singularities and the violation of cosmic censorship, wormholes, and quantum mechanical results as well. In addition, a brief look into the implications for strings is given.

  12. 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.

  13. Negative ion formation processes: A general review

    SciTech Connect

    Alton, G.D.

    1990-01-01

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

  14. 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

  15. THE BIOLOGICAL EFFECTS OF IONIZING RADIATION

    E-print Network

    Slatton, Clint

    Cells (Intestinal tract, Skin) Muscle Cells Nerve CellsLeast Sensitive #12;Damage from Radiation Radiation Damage Occur? #12;Ionization · Ionizing Radiation can remove tightly bound electrons from with neighboring atoms, forming new chemical bonds #12;Interactions with Cell Materials Biological damage occurs

  16. Forensic applications of ambient ionization mass spectrometry.

    PubMed

    Ifa, Demian R; Jackson, Ayanna U; Paglia, Giuseppe; Cooks, R Graham

    2009-08-01

    This review highlights and critically assesses forensic applications in the developing field of ambient ionization mass spectrometry. Ambient ionization methods permit the ionization of samples outside the mass spectrometer in the ordinary atmosphere, with minimal sample preparation. Several ambient ionization methods have been created since 2004 and they utilize different mechanisms to create ions for mass-spectrometric analysis. Forensic applications of these techniques--to the analysis of toxic industrial compounds, chemical warfare agents, illicit drugs and formulations, explosives, foodstuff, inks, fingerprints, and skin--are reviewed. The minimal sample pretreatment needed is illustrated with examples of analysis from complex matrices (e.g., food) on various substrates (e.g., paper). The low limits of detection achieved by most of the ambient ionization methods for compounds of forensic interest readily offer qualitative confirmation of chemical identity; in some cases quantitative data are also available. The forensic applications of ambient ionization methods are a growing research field and there are still many types of applications which remain to be explored, particularly those involving on-site analysis. Aspects of ambient ionization currently undergoing rapid development include molecular imaging and increased detection specificity through simultaneous chemical reaction and ionization by addition of appropriate chemical reagents. PMID:19241065

  17. Negative Influence

    NSDL National Science Digital Library

    William C. Robertson, Ph.D.

    2006-01-01

    This chapter is all about negative numbers, and how to deal with them. They're not all that difficult to understand, but for some reason people get just a little uptight when they see computations involving negative numbers. I'm guessing that the apprehension results from the view that negative numbers mean there are more rules to follow--rules you don't necessarily understand. Well, we'll try and correct that.

  18. 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

  19. Identification of oxidized organic atmospheric species during the Southern Oxidant and Aerosol Study (SOAS) using a novel Ion Mobility Time-of-Flight Chemical Ionization Mass Spectrometer (IMS-ToF-CIMS)

    NASA Astrophysics Data System (ADS)

    Krechmer, J.; Canagaratna, M.; Kimmel, J.; Junninen, H.; Knochenmuss, R.; Cubison, M.; Massoli, P.; Stark, H.; Jayne, J. T.; Surratt, J. D.; Jimenez, J. L.; Worsnop, D. R.

    2013-12-01

    We present results from the field deployment of a novel Ion Mobility Time-of-flight Chemical Ionization Mass Spectrometer (CI-IMS-TOF) during the Southern Oxidant and Aerosol Study (SOAS). IMS-TOF is a 2-dimensional analysis method, which separates gas-phase ions by mobility prior to determination of mass-to-charge ratio by mass spectrometry. Ion mobility is a unique physical property that is determined by the collisional cross section of an ion. Because mobility depends on size and shape, the IMS measurement is able to resolve isomers and isobaric compounds. Additionally, trends in IMS-TOF data space can be used to identify relationships between ions, such as common functionality or polymeric series. During SOAS we interfaced the IMS-TOF to a nitrate ion (NO3-) chemical ionization source that enables the selective ionization of highly oxidized gas phase species (those having a high O:C ratio) through clustering with the reagent ion. Highly oxidized products of terpenes and isoprene are important secondary organic aerosol precursors (SOA) that play an uncertain but important role in particle-phase chemistry. We present several case studies of atmospheric events during SOAS that exhibited elevated concentrations of sulfuric acid and/or organics. These events exhibited a rise in particle number and provide an opportunity to examine the role that organic species may have in local atmospheric new particle formation events. We also present the results from the field deployment and subsequent laboratory studies utilizing a Potential Aerosol Mass (PAM) flow reactor as the inlet for the CI-IMS-TOF. The reactor draws in ambient air and exposes it to high concentrations of the OH radical, created by photolysis O3 in the presence of water. The highly oxidized products are then sampled directly by the CI-IMS-TOF. We performed several experiments including placing pine and deciduous plants directly in front of the reactor opening and observed large increases in the number and concentration of oxidized gas-phase species. Finally, we present preliminary results of atmospheric filter analysis using an Electrospray Ionization (ESI) source interfaced to the IMS-TOF.

  20. 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.

  1. 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

  2. Development of Soft Ionization for Particulate Organic Detection with the Aerodyne Aerosol Mass Spectrometer

    SciTech Connect

    Trimborn, A; Williams, L R; Jayne, J T; Worsnop, D R

    2008-06-19

    During this DOE SBIR Phase II project, we have successfully developed several soft ionization techniques, i.e., ionization schemes which involve less fragmentation of the ions, for use with the Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS). Vacuum ultraviolet single photon ionization was demonstrated in the laboratory and deployed in field campaigns. Vacuum ultraviolet single photon ionization allows better identification of organic species in aerosol particles as shown in laboratory experiments on single component particles, and in field measurements on complex multi-component particles. Dissociative electron attachment with lower energy electrons (less than 30 eV) was demonstrated in the measurement of particulate organics in chamber experiments in Switzerland, and is now a routine approach with AMS systems configured for bipolar, negative ion detection. This technique is particularly powerful for detection of acidic and other highly oxygenated secondary organic aerosol (SOA) chemical functionality. Low energy electron ionization (10 to 12 eV) is also a softer ionization approach routinely available to AMS users. Finally, Lithium ion attachment has been shown to be sensitive to more alkyl-like chemical functionality in SOA. Results from Mexico City are particularly exciting in observing changes in SOA molecular composition under different photochemical/meteorological conditions. More recent results detecting biomass burns at the Montana fire lab have demonstrated quantitative and selective detection of levoglucosan. These soft ionization techniques provide the ToF-AMS with better capability for identifying organic species in ambient atmospheric aerosol particles. This, in turn, will allow more detailed study of the sources, transformations and fate of organic-containing aerosol.

  3. Fluid hydrogen at high density - Pressure ionization

    NASA Technical Reports Server (NTRS)

    Saumon, Didier; Chabrier, Gilles

    1992-01-01

    The Helmholtz-free-energy model for nonideal mixtures of hydrogen atoms and molecules by Saumon and Chabrier (1991) is extended to describe dissociation and ionization in similar mixtures in chemical equilibrium. A free-energy model is given that describes partial ionization in the pressure and temperature ionization region. The plasma-phase transition predicted by the model is described for hydrogen mixtures including such components as H2, H, H(+), and e(-). The plasma-phase transition has a critical point at Tc = 15,300 K and Pc = 0.614 Mbar, and thermodynamic instability is noted in the pressure-ionization regime. The pressure dissociation and ionization of fluid hydrogen are described well with the model yielding information on the nature of the plasma-phase transition. The model is shown to be valuable for studying dissociation and ionization in astrophysical objects and in high-pressure studies where pressure and temperature effects are significant.

  4. Isotope, molecular and surface effects on hyperthermal surface induced dissociated ionization

    Microsoft Academic Search

    A. Danon; A. Amirav

    1993-01-01

    Organic molecules acquired with hyperthermal (1-20 eV) kinetic energy undergo efficient surface ionization. This hyperthermal surface ionization (HSI) may produce both positive and negative ions. The dissociative ionization of alkyl halides results in the production of negative ions of the functional group having high electron affinity, and positive ions of the alkyl radical, which can further dissociate into smaller fragments.

  5. Ultra-high performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry for the analysis of benzimidazole compounds in milk samples.

    PubMed

    Martínez-Villalba, Anna; Moyano, Encarnación; Galceran, Maria Teresa

    2013-10-25

    In this work the atmospheric pressure ionization behavior and the tandem mass spectrometry fragmentation of 19 benzimidazoles was studied. Several atmospheric pressure ionization (API) sources (ESI, APCI and APPI) were evaluated showing that APCI was the best option, mainly for KETO-TCB that provided a 20 times improvement versus ESI. From the studies of tandem mass spectrometry, fragmentation pathways were proposed thus characterizing the most abundant and interesting product ions and selecting the most abundant and selective ones for the confirmatory quantitative method performed in SRM mode in a triple quadrupole mass analyzer. For quantitative analysis, the 19 benzimidazoles were separated in less than 7 min using a C18 column packed with superficially porous particles providing high efficiency within the range of UHPLC. A QuEChERS-like sample treatment was applied to milk samples before the UHPLC-APCI-MS/MS determination providing method limits of quantitation that ranged from 0.6 to 3 ?g kg(-1) and showing good repeatability (RSD: 2-18%) and accuracy (relative errors: 1-23%) suitable for using this method for routine analysis. PMID:24035105

  6. 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

  7. Negative ion spectrometry for detecting nitrated explosives

    NASA Technical Reports Server (NTRS)

    Boettger, H. G.; Yinon, J.

    1975-01-01

    Ionization procedure is modified to produce mainly negative ions by electron capture. Peaks of negative ions are monitored conventionally. Nitrated organic materials could be identified directly from sample sniff inlet stream by suitably modified mass spectrometer because of unique electronegativity which nitro group imparts to organic material.

  8. 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

  9. 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

  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.

    PubMed

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

    2004-11-26

    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 (SPE) and separation by reverse-phase liquid chromatography with gradient elution. The validation data were within the required limits. The assay was successfully applied to authentic plasma samples allowing confirmation of diagnosis of overdose situations as well as monitoring of patients' compliance. PMID:15595665

  11. Direct and simultaneous quantitation of 5-aminolaevulinic acid and porphobilinogen in human serum or plasma by hydrophilic interaction liquid chromatography-atmospheric pressure chemical ionization/tandem mass spectrometry.

    PubMed

    Benton, Christopher M; Couchman, Lewis; Marsden, Joanne T; Rees, David C; Moniz, Caje; Lim, Chang Kee

    2013-02-01

    Serum/plasma concentrations of 5-aminolaevulinic acid (ALA) and porphobilinogen (PBG) are elevated in patients with acute hepatic porphyrias, especially during acute attacks. Current assays require lengthy sample pre-treatment and derivatization steps. We report here a rapid, sensitive and specific hydrophilic interaction liquid chromatography-tandem mass spectrometry method for the direct and simultaneous quantitation of ALA and PBG in serum or plasma following simple protein precipitation with acetonitrile and centrifugation prior to injection. ALA and PBG were detected using selected reaction monitoring mode, following positive atmospheric pressure chemical ionization. Calibration was linear from 0.05 to 50 µmol/L for ALA and PBG. For both analytes, imprecision (relative standard deviation) was <13% and accuracy (percentage nominal concentrations) was between 92 and 107%. The method was successfully applied to the measurement of ALA and PBG in serum or plasma samples for the screening, biochemical diagnosis and treatment monitoring of patients with acute hepatic porphyrias. PMID:23180457

  12. 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

  13. Development and validation of a liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry method for simultaneous analysis of ten amphetamine-, methamphetamine- and 3,4-methylenedioxymethamphetamine-related (MDMA) analytes in human meconium

    PubMed Central

    Kelly, Tamsin; Gray, Teresa R.; Huestis, Marilyn A.

    2008-01-01

    A liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry (LC-APCI-MS/MS) method for quantification of ten amphetamine-related analytes in 1 g meconium is presented. Specimen preparation included homogenization and solid phase extraction. Two multiple reaction monitoring transitions were monitored per analyte. Ten and 1 µL injection volumes permitted quantification up to 10,000 ng/g, with sufficient sensitivity to quantify minor metabolites. Lower limits of quantification ranged from 1.25 to 40 ng/g. Precision was less than 14.2%, with accuracy between 79 – 115%. Meconium from a methamphetamine-exposed neonate was analyzed. Metabolites p-hydroxymethamphetamine, norephedrine and 4-hydroxy-3-methoxymethamphetamine were identified in meconium for the first time. PMID:18424195

  14. 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

  15. 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.

  16. Highly resolved online organic-chemical speciation of evolved gases from thermal analysis devices by cryogenically modulated fast gas chromatography coupled to single photon ionization mass spectrometry.

    PubMed

    Saraji-Bozorgzad, Mohammad R; Eschner, Markus; Groeger, Thomas M; Streibel, Thorsten; Geissler, Robert; Kaisersberger, Erwin; Denner, Thomas; Zimmermann, Ralf

    2010-12-01

    Multi-dimensional analysis (MDA) in analytical chemistry is often applied to improve the selectivity of an analytical device and, therefore, to achieve a better overview of a sample composition. Recently, the hyphenation of thermogravimetry with single photo ionization mass spectrometry (TG-SPIMS) using an electron beam pumped excimer lamp (EBEL) for VUV radiation was applied. The concept of MDA has been realized by upgrading the TG-SPIMS system with a quasi comprehensive chromatographic separation step before the soft ionization (TG-GCxSPIMS). The system was characterized by the thermal analysis of diesel fuel, which has often been investigated by the GCxGC-community and is therefore a well-known sample material in MDA. Data from this measurement are used to explain the three-dimensional data structure and the advantages of the online TG-GCxSPIMS as compared to TG-SPIMS. Subsequently, the thermal decomposition behavior of a polymer, acrylonitrile-butadiene-styrene (ABS), is investigated. TG-GCxSPIMS provides a two-dimensional analysis of the evolved gaseous products. TG relevant data are obtained as well as an improved resolution power to separate isobaric molecular structures without losing any fraction of the samples, as is often the case in heart cutting approaches. Additionally, this solution is not associated with any extension of the measurement time. The assignment of the substance pattern to distinct species is improved as compared to solely using mass spectrometry without a preceding separation step. Furthermore, hitherto undetected compounds have been found in the evolved gases from the thermal degradation of ABS. Finally, a first estimation of the limit of detection has been carried out. This results in a significant decrease of the LOD in case of TG-GCxSPIMS (500 ppt for toluene) as compared to 30 ppb, which could be reached with TG-SPIMS. PMID:21043436

  17. Electron-impact ionization and dissociative ionization of sulfur in the gas phase

    NASA Astrophysics Data System (ADS)

    Zavilopulo, A. N.; Markush, P. P.; Shpenik, O. B.; Mykyta, M. I.

    2014-07-01

    We describe the methods and the results of investigation of the yield of positive ions formed as a result of electron-impact ionization of sulfur. The ionization energy for the basic molecule and the energies corresponding to the emergence of fragment ions are obtained from the ionization efficiency curves. The dynamics of formation of molecular sulfur ions in the temperature range 320-700 K is investigated. The energy dependences of efficiency S n of the ion formation for n = 1-6 are analyzed, and their appearance energies are determined. The total cross section of sulfur ionization by a monochromatic electron beam is also investigated. Using the linear approximation method, we marked out features on the ionization function curve, which correspond to the ionization and excitation energies for multiply charged ions. The total cross section of the formation of negative sulfur ions is measured in the energy range 0-9 eV.

  18. Weakly ionized cosmic gas: Ionization and characterization

    NASA Technical Reports Server (NTRS)

    Rosenberg, M.; Mendis, D. A.; Chow, V. W.

    1994-01-01

    Since collective plasma behavior may determine important transport processes (e.g., plasma diffusion across a magnetic field) in certain cosmic environments, it is important to delineate the parameter space in which weakly ionized cosmic gases may be characterized as plasmas. In this short note, we do so. First, we use values for the ionization fraction given in the literature, wherein the ionization is generally assumed to be due primarily to ionization by cosmic rays. We also discuss an additional mechanism for ionization in such environments, namely, the photoelectric emission of electrons from cosmic dust grains in an interstellar Far Ultra Violet (FUV) radiation field. Simple estimates suggest that under certain conditions this mechanism may dominate cosmic ray ionization, and possibly also the photoionization of metal atoms by the interstellar FUV field, and thereby lead to an enhanced ionization level.

  19. 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...

  20. Implementation and performance evaluation of a database of chemical formulas for the screening of pharmaco/toxicologically relevant compounds in biological samples using electrospray ionization-time-of-flight mass spectrometry.

    PubMed

    Polettini, Aldo; Gottardo, Rossella; Pascali, Jennifer Paola; Tagliaro, Franco

    2008-04-15

    Electrospray ionization (ESI)-time-of-flight (TOF) MS enables searching a wide number of pharmaco/toxicologically relevant compounds (PTRC) in biosamples. However, the number of identifiable PTRC depends on extension of reference database of chemical formulas/compound names. Previous approaches proposed in-house or commercial databases with limitations either in PTRC number or content (e.g., few metabolites, presence of non-PTRC). In the frame of development of a ESI-TOF PTRC screening procedure, a subset of PubChem Compound as reference database is proposed. Features of this database (approximately 50,500 compounds) are illustrated, and its performance evaluated through analysis by capillary electrophoresis (CE)-ESI-TOF of hair/blood/urine collected from subjects under treatment with known drugs or by comparison with reference standards. The database is rich in parent compounds of pharmaceutical and illicit drugs, pesticides, and poisons and contains many metabolites (including about 6000 phase I metabolites and 180 glucuronides) and related substances (e.g., impurities, esters). The average number of hits with identical chemical formula is 1.82 +/- 2.27 (median = 1, range 1-39). Minor deficiencies, redundancies, and errors have been detected that do not limit the potential of the database in identifying unknown PTRC. The database allows a much broader search for PTRC than other commercial/in-house databases of chemical formulas/compound names previously proposed. However, the probability that a search retrieves different PTRC having identical chemical formula is higher than with smaller databases, and additional information (anamnestic/circumstantial data, concomitant presence of parent drug and metabolite, selective sample preparation, liquid chromatographic retention, and CE migration behavior) must be used in order to focus the search more tightly. PMID:18336013

  1. Chemical fingerprint analysis of phenolics of Albizia chinensis based on ultra-performance LC-electrospray ionization-quadrupole time-of-flight mass spectrometry and antioxidant activity.

    PubMed

    Chaudhary, Abha; Kaur, Pushpinder; Kumar, Neeraj; Singh, Bikram; Awasthi, Shiv; Lal, Brij

    2011-11-01

    Albizia species have been shown to have anti-inflammatory and anti-allergic properties. However, efficient analytical methods for identification of their active constituents are still lacking. Ultra-performance liquid chromatography coupled with electrospray ionization-quadrupole time-of-flight mass spectrometry (UPLC-ESI-QTOF-MS) was used to study the phenolic composition of the ethanolic extracts of different parts (flowers, leaves, pods and bark) of A. chinensis. In addition, the antioxidant activity of the ethanolic extracts was evaluated by the 1,1-diphenyl-2-picryl hydrazyl (DPPH) free-radical and 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid (ABTS) radical cation scavenging methods. Four compounds were isolated from the ethanolic extract of the flowers and characterized by 1H and 13C NMR spectroscopy as quercetin-3-O-rhamnoside, quercetin, quercetin-3-O-arabinofuranoside, and myricetin-3-O-rhamnoside. Separation and quantification of the phenolics was accomplished using a reversed-phase BEH C18 column with the mobile phase of methanol-water (0.05% formic acid), and detection wavelengths of 360 and 254 nm. PMID:22224274

  2. 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).

  3. A high efficiency, kinetic-ejection negative ion source for RIB generation

    SciTech Connect

    Alton, G. D.; Liu, Y.; Williams, C.; Murray, S. N. [Physics Division, Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, Tennessee 37831-6368 (United States)

    1999-04-26

    Chemically active radioactive species, diffused from RIB target materials, often arrive at the ionization chamber of the source in a variety of molecular forms. Because of the low probability for simultaneously dissociating and efficiently ionizing the individual atomic constituents of molecules with conventional hot-cathode electron-impact ion sources, the species of interest are often distributed in several mass channels in the form of molecular side-band beams and consequently, their intensities are diluted. The sputter negative ion beam generation technique offers an efficient means for simultaneously dissociating and ionizing highly electronegative atomic species present in molecular carriers. We have incorporated these principles in the design and fabrication of a kinetic ejection negative ion source and evaluated its potential for generating {sup 17,18}F{sup -} beams for the Holifield Radioactive Ion Beam Facility astrophysics research program. The source utilizes Cs{sup +} beams to bombard condensable fluorine compounds that emanate from a target material, such as Al{sub 2}O{sub 3}, and are transported to the cooled inner surface of a conical-geometry cathode where they are adsorbed. The energetic Cs{sup +} beams efficiently dissociate these molecules and sputter their constituents. Since the work functions of cesiated surfaces are low, highly electronegative species such as fluorine are efficiently ionized in the sputter-injection process. Measured efficiencies for ionizing atomic fluorine, dissociated from condensable compounds that are formed by reactions of SF{sub 6} with fibrous Al{sub 2}O{sub 3} material, exceed 6.5%. In this report, we describe the mechanical design features and principles of operation, and present emittance, F{sup -} yield and ionization efficiency data derived from off-line, experimental evaluation of the source.

  4. Addendum to the article: Misuse of null hypothesis significance testing: Would estimation of positive and negative predictive values improve certainty of chemical risk assessment?

    PubMed

    Bundschuh, Mirco; Newman, Michael C; Zubrod, Jochen P; Seitz, Frank; Rosenfeldt, Ricki R; Schulz, Ralf

    2015-03-01

    We argued recently that the positive predictive value (PPV) and the negative predictive value (NPV) are valuable metrics to include during null hypothesis significance testing: They inform the researcher about the probability of statistically significant and non-significant test outcomes actually being true. Although commonly misunderstood, a reported p value estimates only the probability of obtaining the results or more extreme results if the null hypothesis of no effect was true. Calculations of the more informative PPV and NPV require a priori estimate of the probability (R). The present document discusses challenges of estimating R. PMID:25354437

  5. Chemical mutagenesis testing in Drosophila. I. Comparison of positive and negative control data for sex-linked recessive lethal mutations and reciprocal translocations in three laboratories

    SciTech Connect

    Woodruff, R.C.; Mason, J.M.; Valencia, R.; Zimmering, S.

    1984-01-01

    As part of the validation phase of the Drosophila melanogaster segment of the National Toxicology Program, a comparison has been made of positive and negative controls for sex-linked recessive lethal mutations and reciprocal translocations from three laboratories. This comparison involves approximately 700,000 spontaneous recessive lethal mutation tests, 70,000 spontaneous translocation tests, and screens for genetic damage induced by N-nitrosodimethylamine and ..beta..-propiolactone. Spontaneous frequencies for lethal mutations and translocations were homogeneous in the laboratories regardless of solvent or broods sampled. Inhomogeneity was observed in induced frequencies among laboratories, but the variation was no greater than that found within a laboratory.

  6. Low-temperature plasma probe for ambient desorption ionization.

    PubMed

    Harper, Jason D; Charipar, Nicholas A; Mulligan, Christopher C; Zhang, Xinrong; Cooks, R Graham; Ouyang, Zheng

    2008-12-01

    A low-temperature plasma (LTP) probe has been developed for ambient desorption ionization. An ac electric field is used to induce a dielectric barrier discharge through use of a specially designed electrode configuration. The low-temperature plasma is extracted from the probe where it interacts directly with the sample being analyzed, desorbing and ionizing surface molecules in the ambient environment. This allows experiments to be performed without damage to the sample or underlying substrate and, in the case of biological analysis on skin surfaces, without electrical shock or perceptible heating. Positive or negative ions are produced from a wide range of chemical compounds in the pure stateand as mixtures in the gaseous, solution, or condensed phases, using He, Ar, N2, or ambient air as the discharge gas. Limited fragmentation occurs, although it is greater in the cases of the molecular than the atomic discharge gases. The effectiveness of the LTP probe has been demonstrated by recording characteristic mass spectra and tandem mass spectra of samples containing hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) from poly(tetrafluoroethylene) (PTFE) surfaces where limits of detection are as low as 5 pg. Other performance characteristics, when using a commercial ion trap mass spectrometer, include 3-4 orders of magnitude linear dynamic range in favorable cases. Demonstration applications include direct analysis of cocaine from human skin, determination of active ingredients directly in drug tablets, and analysis of toxic and therapeutic compounds in complex biological samples. Ionization of chemicals directly from bulk aqueous solution has been demonstrated, where limits of detection are as low as 1 ppb. Large surface area sampling and control of fragmentation by a simple adjustment of the electrode configuration during operation are other demonstrated characteristics of the method. PMID:19551980

  7. 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.

  8. Development of a liquid chromatography-electrospray chemical ionization tandem mass spectrometry analytical method for analysis of eleven hydroxylated polybrominated diphenyl ethers.

    PubMed

    Feo, Maria Luisa; Barón, Enrique; Aga, Diana S; Eljarrat, Ethel; Barceló, Damià

    2013-08-01

    Recently, hydroxylated polybrominated diphenyl ethers (OH-PBDEs) have emerged as environmentally relevant pollutants due to recent reports of their natural production and metabolism. Recent mechanistic studies in human and rats have shown that some OH-PBDEs are more potent than parent compounds (PBDEs) and may contribute substantially to neurodevelopmental disorders by direct neurotoxicity, or indirectly through altered thyroid disruption. However, analytical methodologies for determination of OH-PBDEs are currently limited. In this study a robust liquid chromatography-electrospray tandem triple quadrupole-linear ion trap mass spectrometer (LC-ESI-QqLIT-MS-MS) in negative mode method was developed for the determination of eleven OH-tri- to OH-hexa-PBDEs. Two different columns were tested and compared for chromatographic separation: a C18 BetaBasic and a Purospher STAR RP 18, working at pH 8 and 10, respectively. Mobile phase (acetonitrile:water) was optimized by changing the pH of the aqueous phase and the concentration of the organic modifier (methanol). The MS-MS parameters (declustering potential (DP), collision energy (CE) and cell exit potential (CXP)) were optimized. Selected reaction monitoring (SRM) was used in order to increase sensitivity. Two SRM transitions ([M-H](-)>[Br](-)) were selected for each OH-PBDE, one for quantification and the second one for confirmation. Under the optimized conditions, the instrumental limits of detection were between 0.17 and 0.72injectedpg. The method provided good linearity (r>0.99 for a concentration range of 0.30-100ng/mL), accuracy and precision (%Dev and %RSD?20% for intra- and inter-assays). PMID:23791149

  9. Semiclassical propagation method for tunneling ionization

    NASA Astrophysics Data System (ADS)

    Fabrikant, Ilya I.; Gallup, Gordon A.

    2009-01-01

    We apply the semiclassical propagation technique to tunneling ionization in atomic and molecular systems. Semiclassical wave functions and the tunneling flux are calculated from the solution of the classical equations of motion in the complex time plane. We illustrate this method by rederiving the known result for the decay rate of a negative ion in a weak electric field. We then obtain numerical results for atomic hydrogen, H2+ , H2 , and Ar, and compare them with the results of the asymptotic [Ammosov-Delone-Krainov (ADK)] theory. The asymptotic theory gives surprisingly good results for the atomic and molecular ionization rates. In particular, our calculations for the simplest case of molecular suppression, ionization of H2 versus Ar, confirms the ADK analysis of Tong [Phys. Rev. A 66, 013409 (2002)], explaining that the suppression is mainly due to the different symmetries of the ionized orbitals, s in H2 and 3pz in Ar.

  10. Semiclassical propagation method for tunneling ionization

    NASA Astrophysics Data System (ADS)

    Fabrikant, Ilya; Gallup, Gordon

    2009-05-01

    We apply the semiclassical propagation technique to tunneling ionization in atomic and molecular systems. Semiclassical wave functions and the tunneling flux are calculated from the solution of the classical equations of motion in the complex time plane. We illustrate this method by rederiving the known result for the decay rate of a negative ion in a weak electric field. We then obtain numerical results for atomic hydrogen, H2^+, H2 and Ar, and compare them with the results of the asymptotic (ADK) theory. The asymptotic theory gives surprisingly good results for the atomic and molecular ionization rates. In particular, our calculations for the simplest case of molecular suppression, ionization of H2 versus Ar, confirms the ADK analysis of Tong et al, Phys. Rev. A 66, 013409 (2002) explaining that the suppression is mainly due to the different symmetries of the ionized orbitals, s in H2 and 3pz in Ar.

  11. Ionization Energies of Lanthanides

    ERIC Educational Resources Information Center

    Lang, Peter F.; Smith, Barry C.

    2010-01-01

    This article describes how data are used to analyze the pattern of ionization energies of the lanthanide elements. Different observed pathways of ionization between different ground states are discussed, and the effects of pairing, exchange, and orbital interactions on ionization energies of the lanthanides are evaluated. When all the above…

  12. 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 ...

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

    SciTech Connect

    Creaser, R.A.; Papanastassiou, D.A.; Wasserburg, G.J. (California Institute of Technology, Pasadena (USA))

    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 OsO{sub 3}{sup {minus}}, ReO{sub 4}{sup {minus}}, and IrO{sub 2}{sup {minus}}. The sharp distinction in the masses of the dominant molecular species produced by this technique permits the measurement of isotopic compositions of each element from mixtures of platinum-group elements without significant isobaric interferences. For {sup 187}Re-{sup 187}Os isotope studies, this technique offers the advantage of isotopic analyses without prior chemical separation of Re from Os, as no isobaric interference between the oxides of {sup 187}Os and {sup 187}Re exists under these conditions. For 4 ng Os, stable ion currents of 3 {times} 10{sup {minus}12} A can be maintained for over one hour, which allows determination of isotopic ratios with a Faraday collector to a precision of better than {plus minus}2{per thousand} (2 {sigma}{sub m}). For 70 pg Os, isotopic ratios can be measured with a precision of better than {plus minus}5{per thousand} using a secondary electron multiplier. The detection limit for Os is estimated to be below 10{sup {minus}14} g. Osmium isotopic ratios have also been determined by direct loading of natural iridosmine with a precision of {plus minus}0.5{per thousand} or better. They have obtained ionization efficiencies of 2-6% for Os and >20% for Re; these are superior to those reported for other techniques available to data, and demonstrate that negative thermal ion mass spectrometry will have widespread application to {sup 187}Re-{sup 187}Os chronometry and to studies of the geochemistry and environmental chemistry of the platinum-group elements.

  14. 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.

  15. A switchable reagent ion high resolution time-of-flight chemical ionization mass spectrometer for real-time measurement of gas phase oxidized species: characterization from the 2013 Southern Oxidant and Aerosol Study

    NASA Astrophysics Data System (ADS)

    Brophy, P.; Farmer, D. K.

    2015-03-01

    A novel configuration of the Aerodyne high resolution time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS) as a switchable reagent ion (SRI) HR-TOF-CIMS is presented and described along with data collected at the Southern Oxidant and Aerosol Study (SOAS) during the summer of 2013. The calibration system and reduced pressure gas-phase inlet are characterized. The average limit of detection and limit of quantification for formic acid during SOAS are 82 and 863 ppt, respectively, corresponding to an average sensitivity of 13 ± 5 Hz ppt-1. Hourly background determinations and calibrations are shown to be essential for tracking instrument performance and accurately quantifying formic acid. Maximum daytime formic acid concentrations of 10 ppb are reported during SOAS, and a strong diel cycle is observed leading to night time concentrations below the limit of quantification. Other species presented exhibit diel behavior similar to formic acid. The concept of the mass defect enhancement plot and the use of signal-to-noise are described in detail as a method for investigating HR-TOF-CIMS spectra in an effort to reduce data complexity.

  16. Quantitation of spectinomycin residues in bovine tissues by ion-exchange high-performance liquid chromatography with post-column derivatization and confirmation by reversed-phase high-performance liquid chromatography-atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

    Hornish, R E; Wiest, J R

    1998-07-01

    Determinative and confirmatory methods of analysis for spectinomycin residue in bovine kidney, liver, muscle and fat have been developed. The determinative method is a single-column HPLC ion-exchange procedure that incorporates a two-step post-column oxidation of the secondary amines to primary amines followed by derivatization with o-phthalaldehyde. The method was validated in all tissues to a low-end concentration of 0.10 micrograms/g (limit of quantitation) and to a high-end of 10 micrograms/g for kidney, which is the rate-limiting tissue for residues of spectinomycin. The recovery of spectinomycin from all tissues was > 80% and the variability (R.S.D.) was generally < 10%. For liver, an alternative reversed-phase HPLC separation was required for incurred-residue samples. The confirmatory method employed an atmospheric pressure chemical ionization-MS-MS approach utilizing a rapid reversed-phase HPLC system with a mobile phase of methanol and 1% acetic acid. The protonated molecular ion for spectinomycin at m/z 333 produced four diagnostic reaction-product ions at 98, 116, 158 and 189 for confirmation. The method was validated to a lower limit of confirmation of 0.10 micrograms/g. PMID:9691313

  17. Negative ion mass spectrometry and the detection of carbonyls and HCN from clover

    NASA Astrophysics Data System (ADS)

    Custer, Thomas G.; Kato, Shuji; Fall, Ray; Bierbaum, Veronica M.

    2000-12-01

    We have demonstrated that negative ion-chemical ionization mass spectrometry (NI-CIMS) can be used to distinguish several isomeric volatile organic compounds (VOCs) that are emitted from wounded plants. Reaction chemistry with HO-, hydrogen/deuterium exchange patterns, and collision-induced dissociation spectra allow identification of the isomers. Laboratory studies of emissions from wounded clover using NI-CIMS show several previously detected VOCs, but also clearly demonstrate the emission of HCN. This compound is presumably formed by the decomposition of cyanogenic glycosides which also form aldehyde and ketone byproducts. These results suggest that NI-CIMS may be a valuable tool for investigating VOCs and HCN release from vegetation.

  18. Recent advances in negative ion mass spectrometry.

    PubMed Central

    Bowie, J H

    1980-01-01

    The paper describes theoretical and applied applications of negative ion chemistry carried out at Adelaide during the past five years. kinetic energy release in negative metastable ion decompositions is described, with particular reference to simple cleavage reactions, rearrangement reactions, and reactions which proceed by dual mechanisms. The application of deuterium isotope effects as a mechanistic probe is illustrated by reference to the elimination of ketene from quinone acetate negative ions. Charge stripping of a negative ion yields a decomposing positive ion, which produces a dissociative charge inversion spectrum of the negative ion. This technique allows the study of positive ions not available by conventional ionization; it provides a fingerprint for the parent positive ion produced in the collision process, and it may be used to determine the structure of the precursor negative ion. Finally, a combination of a negative ion spectrum and a charge inversion spectrum may be used as an analytical technique for the structure determination of unknown molecules. PMID:7428749

  19. Atmospheric pressure ionization and gas phase ion mobility studies of isomeric dihalogenated benzenes using different ionization techniques

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

    Ion mobility spectrometry (IMS) featuring different ionization techniques was used to analyze isomeric ortho-, meta- and para-dihalogenated benzenes in order to assess how structural features affect ion formation and drift behavior. The structure of the product ions formed was investigated by atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and IMS-MS coupling. Photoionization provided [M]+ ions for chlorinated and fluorinated compounds while bromine was cleaved from isomers of dibromobenzene and bromofluorobenzene. This ionization technique does not permit the different isomers to be distinguished. Comparable ions and additional clustered ions were obtained using 63Ni ionization. Depending on the chemical constitution, different clustered ions were observed in ion mobility spectra for the separate isomers of dichlorobenzene and dibromobenzene. Corona discharge ionization permits the most sensitive detection of dihalogenated compounds. Only clustered product ions were obtained. Corona discharge ionization enables the classification of different structural isomers of dichlorobenzene, dibromobenzene and bromofluorobenzene.

  20. Analytical formulation of ionization source term for discharge models in argon, helium, nitrogen, and silane

    Microsoft Academic Search

    N. Ouadoudi; L. C. Pitchford; J. P. Boeuf

    1992-01-01

    Simple analytical representations of the ionization source terms in argon, helium, nitrogen, and silane dc glow discharges for steady-state and quasisteady-state conditions are presented. These analytical forms express well the highly nonequilibrium nature of the ionization in the cathode fall and negative glow regions which cannot be described by a Townsend ionization coefficient depending on the local value of the

  1. [Fe IV] emission in ionized nebulae

    E-print Network

    Monica Rodriguez

    2003-02-25

    This paper presents an analysis of [Fe IV] emission based on new identifications and previous measurements of [Fe IV] lines in 30 Doradus, IC 4846, M42, SMC N88A, and SBS 0335-052. The Fe abundances obtained by adding the abundances of the relevant Fe ions (mainly Fe^{++} and Fe^{3+}) are found to be lower, by factors in the range 2.6-5.9, than the Fe abundances implied by [Fe III] emission and an ionization correction factor derived from ionization models. The most likely explanation of this discrepancy is that either the collision strengths for [Fe IV] or the Fe ionization fractions predicted by models are unreliable. The available data neither allow one to distinguish between these two possibilities nor to exclude another possible explanation: that the discrepancy implies the presence of a gradient in the Fe abundance within the ionized gas. Further measurements of [Fe IV] lines and checks on the Fe^{3+} atomic data and ionization models are needed to reach a definitive conclusion. The discrepancy introduces an uncertainty in the determination of Fe abundances in ionized nebulae. This uncertainty has implications for our understanding of both the evolution of dust in ionized nebulae and the chemical history of low metallicity galaxies.

  2. 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.

  3. 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.

  4. An improved dispersive solid-phase extraction clean-up method for the gas chromatography-negative chemical ionisation tandem mass spectrometric determination of multiclass pesticide residues in edible oils.

    PubMed

    Deme, Pragney; Azmeera, Tirupathi; Prabhavathi Devi, B L A; Jonnalagadda, Padmaja R; Prasad, R B N; Vijaya Sarathi, U V R

    2014-01-01

    An improved sample preparation using dispersive solid-phase extraction clean-up was proposed for the trace level determination of 35 multiclass pesticide residues (organochlorine, organophosphorus and synthetic pyrethroids) in edible oils. Quantification of the analytes was carried out by gas chromatography-mass spectrometry in negative chemical ionisation mode (GC-NCI-MS/MS). The limit of detection and limit of quantification of residues were in the range of 0.01-1ng/g and 0.05-2ng/g, respectively. The analytes showed recoveries between 62% and 110%, and the matrix effect was observed to be less than 25% for most of the pesticides. Crude edible oil samples showed endosulfan isomers, p,p'-DDD, ?-cypermethrin, chlorpyrifos, and diazinon residues in the range of 0.56-2.14ng/g. However, no pesticide residues in the detection range of the method were observed in refined oils. PMID:24001824

  5. Martian Meteor Ionization Layers

    NASA Technical Reports Server (NTRS)

    Grebowsky, J. M.; Pesnell, W. D.

    1999-01-01

    Small interplanetary grains bombard Mars, like all the solar system planets, and, like all the planets with atmospheres, meteoric ion and atom layers form in the upper atmosphere. We have developed a comprehensive one-dimensional model of the Martian meteoric ionization layer including a full chemical scheme. A persistent layer of magnesium ions should exist around an altitude of 70 km. Unlike the terrestrial case, where the metallic ions are formed via charge-exchange with the ambient ions, Mg(+) in the Martian atmosphere is produced by photoionization. Nevertheless, the predicted metal layer peak densities for Earth and Mars are similar. Diffusion solutions, such as those presented here, should be a good approximation of the metallic ions in regions where the magnetic field is negligible and may provide a significant contribution to the nightside ionosphere. The low ultraviolet absorption of the Martian atmosphere may make Mars an excellent laboratory in which to study meteoric ablation. Resonance lines not seen in the spectra of terrestrial meteors may be visible to a surface observatory in the Martian highlands.

  6. 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.

  7. Screening, library-assisted identification and validated quantification of 23 benzodiazepines, flumazenil, zaleplone, zolpidem and zopiclone in plasma by liquid chromatography/mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Kratzsch, Carsten; Tenberken, Oliver; Peters, Frank T; Weber, Armin A; Kraemer, Thomas; Maurer, Hans H

    2004-08-01

    A liquid chromatographic/mass spectrometric assay with atmospheric pressure chemical ionization (LC/APCI-MS) is presented for fast and reliable screening and identification and also for precise and sensitive quantification in plasma of the 23 benzodiazepines alprazolam, bromazepam, brotizolam, camazepam, chlordiazepoxide, clobazam, clonazepam, diazepam, flunitrazepam, flurazepam, desalkylflurazepam, lorazepam, lormetazepam, medazepam, metaclazepam, midazolam, nitrazepam, nordazepam, oxazepam, prazepam, temazepam and tetrazepam, triazolam, their antagonist flumazenil and the benzodiazepine BZ1 (omega 1) receptor agonists zaleplone, zolpidem and zopiclone. It allows confirmation of the diagnosis of an overdose situation and monitoring of psychiatric patients' compliance. The analytes were isolated from plasma using liquid-liquid extraction and were separated on a Merck LiChroCART column with Superspher 60 RP Select B as the stationary phase. Gradient elution was performed using aqueous ammonium formate and acetonitrile. After screening and identification in the scan mode using the authors' LC/MS library, the analytes were quantified in the selected-ion monitoring mode. The quantification assay was fully validated. It was found to be selective proved to be linear from sub-therapeutic to over therapeutic concentrations for all analytes, except bromazepam. The corresponding reference levels the assay's accuracy and precision data for all studied substances are listed. The accuracy and precision data were within the required limits with the exception of those for bromazepam. The analytes were stable in frozen plasma for at least 1 month. The validated assay was successfully applied to several authentic plasma samples from patients treated or intoxicated with various benzodiazepines or with zaleplone, zolpidem or zopiclone. It has proven to be appropriate for the isolation, separation, screening, identification and quantification of the drugs mentioned above in plasma for clinical toxicology, e.g. in cases of poisoning, and forensic toxicology, e.g. in cases of driving under the influence of drugs. PMID:15329838

  8. 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

  9. An improved high performance liquid chromatography-photodiode array detection-atmospheric pressure chemical ionization-mass spectrometry method for determination of chlorophylls and their derivatives in freeze-dried and hot-air-dried Rhinacanthus nasutus (L.) Kurz.

    PubMed

    Kao, Tsai Hua; Chen, Chia Ju; Chen, Bing Huei

    2011-10-30

    Rhinacanthus nasutus (L.) Kurz, a traditional Chinese herb possessing antioxidant and anti-cancer activities, has been reported to contain functional components like carotenoids and chlorophylls. However, the variety and amount of chlorophylls remain uncertain. The objectives of this study were to develop a high performance liquid chromatography-photodiode array detection-atmospheric pressure chemical ionization-mass spectrometry (HPLC-DAD-APCI-MS) method for determination of chlorophylls and their derivatives in hot-air-dried and freeze-dried R. nasutus. An Agilent Eclipse XDB-C18 column and a gradient mobile phase composed of methanol/N,N-dimethylformamide (97:3, v/v), acetonitrile and acetone were employed to separate internal standard zinc-phthalocyanine plus 12 cholorophylls and their derivatives within 21 min, including chlorophyll a, chlorophyll a', hydroxychlorophyll a, 15-OH-lactone chlorophyll a, chlorophyll b, chlorophyll b', hydroxychlorophyll b, pheophytin a, pheophytin a', hydroxypheophytin a, hydroxypheophytin a' and pheophytin b in hot-air-dried R. nasutus with flow rate at 1 mL/min and detection at 660 nm. But, in freeze-dried R. nasutus, only 4 chlorophylls and their derivatives, including chlorophyll a, chlorophyll a', chlorophyll b and pheophytin a were detected. Zinc-phthalocyanine was found to be an appropriate internal standard to quantify all the chlorophyll compounds. After quantification by HPLC-DAD, both chlorophyll a and pheophytin a were the most abundant in hot-air-dried R. nasutus, while in freeze-dried R. nasutus, chlorophyll a and chlorophyll b dominated. PMID:22063550

  10. 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.

  11. Electrization of aerosol wetted in bipolarly ionized air

    NASA Astrophysics Data System (ADS)

    Smirnov, V. V.

    2010-06-01

    We studied the influence of the characteristics of the atmospheric ionization and physical-chemical state of condensation nuclei on the electric state of convective cells. Based on the results of experiments in an adiabatic chamber with a volume of 3200 m3, we found that, with increase in relative air humidity H from 40 to 95% with an equivalent ascent rate of 100-400 cm/s, excessive charges in amounts of about 103 or more elementary charges per cm3 may be accumulated on the nuclei. The sign of the charge depends on the chemical composition of the hygroscopic nuclei. For instance, media with insoluble nuclei (porous silica, etc.) typically have prevailing negative charges; those with soluble nuclei (sodium chloride, etc.) are dominated by positive charges. At H = 60-90%, the electrization of soluble nuclei can be interpreted in the diffusion-kinetic models of the ion charging of aerosols. Considerable negative volume charges, which appear on insoluble hygroscopic nuclei during a rise in humidity from 40 to 70%, are explained by the structuring of surface water films, which exhibit a resemblance to negative lightweight ions. At high values ( H > 90%), it is necessary to take into account the resemblance of the wetted surfaces to positive lightweight ions. We showed for the first time that, at ion formation rates of 3 and 1010 ion pairs/(cm3 s), the differences in the volume charge and wetting rate of condensation nuclei are insignificant. It is concluded that, in many meteorological situations, the first stage of electrization of the convection-derived cloud media is the ion charging of the condensation nuclei.

  12. 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

  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. 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...

  15. 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.

  16. Pharmacokinetics screening for multi-components absorbed in the rat plasma after oral administration of traditional Chinese medicine Flos Lonicerae Japonicae-Fructus Forsythiae herb couple by sequential negative and positive ionization ultra-high-performance liquid chromatography/tandem triple quadrupole mass spectrometric detection.

    PubMed

    Zhou, Wei; Tam, Kin Y; Meng, Minxin; Shan, Jinjun; Wang, Shouchuan; Ju, Wenzheng; Cai, Baochang; Di, Liuqing

    2015-01-01

    The current study aims to investigate the pharmacokinetics of multi-components (caffeic acid, quinic acid, genistein, luteolin, quercetin, neochlorogenic acid, chlorogenic acid, cryptochlorogenic acid, arctigenin, genistin, luteoloside, astragalin, hyperoside, isoquercitrin, 3,5-dicaffeoylquinic acid, 3,4-dicaffeoylquinic acid, rutin, loganin, pinoresinol-?-d-glucoside, phillyrin, isoforsythoside, forsythoside A and forsythoside B) following oral administration of Flos Lonicerae Japonicae-Fructus Forsythiae herb couple in rats. A rapid and sensitive UPLC-ESI-MS/MS with sequential positive and negative ionization modes was developed to determine the 23 absorbed ingredients using one sample preparation combined with three chromatographic conditions in rat plasma. After mixing with internal standard (IS) (tinidazole and chloramphenicol), samples were pretreated by liquid-liquid extraction (LLE) with n-butyl alcohol/ethyl acetate (1:1, v/v). The separations for pinoresinol-?-d-glucoside, phillyrin, isoforsythoside, forsythoside A and forsythoside B were performed on an ACQUITY UPLC BEH C18 column (100mm×2.1mm, 1.7?m) with acetonitrile/methanol (4:1, v/v)-water as mobile phase. For analyzing quinic acid, an ACQUITY UPLC HSS T3 column (100mm×2.1mm, 1.8?m) was applied with acetonitrile/methanol (4:1, v/v)-0.01% formic acid as mobile phase after dilution up to 25-fold. The same column was applied to the other components with acetonitrile/methanol (4:1, v/v)-0.4% formic acid as mobile phase. The method validation results demonstrated that the proposed method was sensitive, specific and reliable, which was successfully applied to the pharmacokinetic study of the multi-components after oral administration of Flos Lonicerae Japonicae-Fructus Forsythiae herb couple. PMID:25533397

  17. 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.

  18. 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

  19. Quantum tunnelling and classical above-barrier transitions in electron detachment from negative ions by negatively charged projectiles

    Microsoft Academic Search

    V. N. Ostrovsky; K. Taulbjerg

    1996-01-01

    A simple model of electron detachment from negative ions by negatively charged projectile impact is developed as a combination of quantum tunnelling and classical field ionization. While the tunnelling theory has been discussed previously by Smirnov and Chibisov, we have substantially amended Solov'ev's classical model for above-barrier transition. As the most important modification we introduce the concept of decay rate

  20. Triboelectric spray ionization.

    PubMed

    Özdemir, Abdil; Lin, Jung-Lee; Gillig, Kent J; Chen, Chung-Hsuan

    2013-02-01

    Triboelectric spray ionization (TESI) is a variation of electrospray ionization (ESI) using common instrumental components, including gas flow, solvent flow rate and heat, the only difference being the use of a high-voltage power supply for ESI or a static charge for TESI. The ionization of solvent or analyte is due to the electrostatic potential difference formed between the spray electrode and counter electrode. The ion source contains a pneumatic spray operated over a range of flow rates (0.15-1.5 µl/min) and gas pressures (0-100). This new design contains a standalone spray assembly and an optional metal mesh in front of the spray. There are several parameters that affect the performance during ionization of molecules including the flow rate of solvent, gas pressure, temperature, solvent acidity, distance and potential difference between emitter and counter electrode. A variable electrostatic potential can be applied for higher ionization efficiency. The new ionization method was successfully applied to solutions of various proteins under different conditions. The same charge-state distributions compared to other ESI techniques are observed for all the protein samples. The unique feature of TESI is very efficient spraying by using a natural electrostatic potential even at the potential that a human body can produce. This provides very gentle ionization efficiency of peptides and proteins in different solvents. PMID:23378087

  1. Time Resolved Studies of Interfacial Reactions of Ozone with Pulmonary Phospholipid Surfactants Using Field Induced Droplet Ionization Mass Spectrometry

    E-print Network

    Goddard III, William A.

    Using Field Induced Droplet Ionization Mass Spectrometry Hugh I. Kim,, Hyungjun Kim,,§,| Young Shik Shin ionization mass spectrometry (FIDI-MS) comprises a soft ionization method to sample ions from the surface-liquid interface in negative ion mode using FIDI mass spectrometry. Our results demonstrate unique characteristics

  2. Practical Aspects of Electron Ionization

    Microsoft Academic Search

    Jürgen H. Gross; Mass Spectrometry

    \\u000a The use of electron ionization (EI) [1] dates back to the infancy of mass spectrometry in the early 20th century. Before, only spark source (SS), glow discharge (GD), and thermal ionization (TI) had been in use (Chap. 15) [2]. In electron ionization, energetic electrons are shot onto gaseous neutrals to effect\\u000a their ionization.

  3. 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

  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. Positron ionization mass spectrometry: An organic mass spectrometrist's view

    SciTech Connect

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

    1990-01-01

    We are currently engaged in a research program to study the ionization of polyatomic molecules by positrons. We refer to the technique herein as positron ionization mass spectrometry which includes all of the possible ionization mechanisms. In the course of this work we will attempt to characterize each of the important ionization mechanisms. Our ultimate objective is to explore the use of positron ionization mass spectrometry for chemical analysis. Several other groups have also begun to pursue aspects of positron ionization in parallel with our efforts although with somewhat different approaches and, perhaps with slightly different emphases. Recently, for example, Passner et al. have acquired mass spectra in a Penning trap resulting from the ionization of several different polyatomic molecules by near thermal kinetics energy positrons. Our research involves studying the different types of ionizing interactions of positrons with organic molecules, as a function of positron kinetic energy. For ionization of polyatomic molecules by positrons, several possible mechanisms are apparent from lifetime and scattering cross-section data. These mechanisms are discussed.

  6. 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

  7. 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.

  8. Instability of ionization equilibrium of a weakly ionized three-component plasma

    NASA Astrophysics Data System (ADS)

    Gitterman, M.; Steinberg, V.

    1979-09-01

    The general stability conditions of a three-component plasma lead, in addition to the usual critical phenomena, to the appearance of a chemical instability, connected with the multiple solution of the law of mass action. As a result of a first-order transition the system will separate into two phases with different degrees of ionization. As the fraction of highly ionized phase increases, the conductivity of the system becomes metallic. Such a phenomenon can explain the metal-dielectric transition and its connection with such critical phenomena in different systems as weak electrolytes, molten salts, metal-ammonia solutions, and solid-state plasmas.

  9. WARPED IONIZED HYDROGEN IN THE GALAXY

    SciTech Connect

    Cersosimo, J. C.; Figueroa, N. Santiago; Velez, S. Figueroa; Soto, C. Lozada [Department of Physics and Electronics, University of Puerto Rico at Humacao, Humacao, PR 00791 (Puerto Rico); Mader, S. [CSIRO Parkes Observatory, New South Wales (Australia); Azcarate, D. [Instituto Argentino de RadioastronomIa, CC No. 5, 1894 Villa Elisa. BsAs (Argentina)], E-mail: juan.cersosimo@upr.edu

    2009-07-01

    We report observations of the H166{alpha} ({nu} = 1424.734 MHz) radio recombination line (RRL) emission from the Galactic plane in the longitude range l = 267 deg. - 302 deg. and latitude range b = -3.{sup 0}0 to +1.{sup 0}5. The line emission observed describes the Carina arm in the Galactic azimuth range from {theta} = 260 deg. to 190 deg. The structure is located at negative latitudes with respect to the formal Galactic plane. The observations are combined with RRL data from the first Galactic quadrant. Both quadrants show the signature of the warp for the ionized gas, but an asymmetry of the distribution is noted. In the fourth quadrant, the gas is located between Galactic radii R {approx} 7 and 10 kpc, and the amplitude of the warp is seen from the midplane to z {approx} -150 pc. In the first quadrant, the gas is found between R {approx} 8 and 13-16 kpc, and flares to z {approx} +350 pc. We confirm the warp of the ionized gas near the solar circle. The distribution of the ionized gas is compared with the maximum intensity H I emission (0.30 < n{sub HI} < 0.45 cm{sup -3}) at intervals of the Galactic ring. The ionized material is correlated with the H I maximum intensity in both quadrants, and both components show the same tilted behavior with respect to the mid-Galactic plane.

  10. 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.

  11. 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.

  12. Dow and Kaw,eff vs. Kow and K°aw: Acid\\/base ionization effects on partitioning properties and screening commercial chemicals for long-range transport and bioaccumulation potential

    Microsoft Academic Search

    Sierra Rayne; Kaya Forest

    2010-01-01

    A set of 543 ionizable commercial organic compounds with various acid\\/base functionalities and experimental octanol-water partitioning coefficients (log Kow) were obtained from the Canadian Domestic Substances List. Corresponding pH-dependent octanol-water distribution coefficients (log Dow) and air-water partitioning coeffients (log Kaw,eff) were estimated using the SPARC software program, as were log Kow and log K°aw values for the neutral forms of

  13. Method of forming a chemical composition

    DOEpatents

    Bingham, Dennis N. (Idaho Falls, ID); Wilding, Bruce M. (Idaho Falls, ID); Klingler, Kerry M. (Idaho Falls, ID); Zollinger, William T. (Idaho Falls, ID); Wendt, Kraig M. (Idaho Falls, ID)

    2007-10-09

    A method of forming a chemical composition such as a chemical hydride is described and which includes the steps of selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of hydrogen; and exposing the selected composition to an amount of ionizing radiation to encourage the changing of the chemical bonds of the selected composition, and chemically reacting the selected composition with the source of hydrogen to facilitate the formation of a chemical hydride.

  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. Electrospray Ionization Mass Spectrometry of hexanitrohexaazaisowurtzitane (CL-20)

    SciTech Connect

    Campbell, James A.; Szecsody, Jim E.; Devary, Brooks J.; Valenzuela, Blandina R.

    2007-09-03

    Hexanitrohexaazaisowurtzitane, (C6H6N12O12, MW 438) {CL-20}, is a high-energy propellent that has been recently developed and successfully tested (Nielsen et al. 1998). CL-20 releases more energy on ignition and is more stable to accidental detonation than currently used energetic materials. It is expected to replace many of the energetic materials currently being used by the Department of Defense (DoD). The EPA method 8330 (EPA 1997) for the analysis of explosives and metabolites in soils calls for the use of UV/Vis detection. High performance liquid chromatography has been used to quantify CL-20 and precursor concentration (Bazaki et al. 1998`) at relatively high concentrations. Fourier transform infrared (FTIR) spectroscopy has been used to identify different crystal forms of CL-20 (4 isomers; Kim et al. 1998). Campbell et al. (1997) utilized particle beam mass spectrometry for the analysis of enzymatic degradation of explosives. Introduction and recent improvements of ionization techniques such as electrospray (ES) have allowed the mass spectrometer to become more widely used in liquid chromatography. Schilling(1996) also examined explosive components and metabolites using electrospray (ES) and atmospheric pressure chemical ionization (APCI) liquid chromatography/mass spectrometry (LC/MS). Schilling’s results showed that compared to thermospray LC/MS, APCI and ES were more sensitive than thermospray by at least an order of magnitude. 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 10 nitroso-RDX metabolites, and other munitions in ground water have been analyzed using solid phase extraction and isotope dilution liquid chromatography-APCI mass spectrometry (Cassada et al. 1999). The method detection limits indicate that nitramine and nitroaromatic compounds can be routinely determined in ground water samples using electrospray LC/MS with concentration techniques utilizing solid-phase extraction. Miller et al. (1996) studied nitrated explosives with mobile phase additives to enhance the ESI intensities and spectral consistencies. Several of the explosives gave nitrate adduct ions in the negative mode with ammonium nitrate as the mobile phase. The nitramines RDX and 1,3,5,7-tetranitro-1,3,5,7 tetraazacyclooctane (HMX) showed the greatest enhancement in response of the explosives. Ammonium nitrate was used as the mobile phase and made it possible to obtain consistent and interpretable LC/MS spectra at the nanogram level. Campbell et al. (1999), Shi et al. (2000), and Goheen et al. (1999) utilized electrospray ionization mass spectrometry for the identification of degradation products of explosives. Yinon et al. (1997) used ESI and tandem mass spectrometry collision-induced dissociation to examine several nitramine compounds including trinitrotolutene (TNT), RDX, and pentaerythritol tetranitrate (PETN). The results indicate that explosives can be detected in the negative ion mode and characterized by various adduct ions. As an example, for nitroglycerin, the major adduct ion observed was (M+ONO2)-. In addition, Harvey et al. (1992) have used direct probe mass spectrometry for the analysis of degradation products of tetryl and its transformation products in soil. The negative ion electrospray mass spectrum of CL-20 is reported here. The major adduct ions observed under negative ion conditions were (M+Cl)- at m/z 473 and (M+ONO2) – at m/z 500. In addition, the results of mass spectrometry/mass spectrometry studies are also discussed.

  16. 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

  17. Ionizing radiation from tobacco

    SciTech Connect

    Westin, J.B.

    1987-04-24

    Accidents at nuclear power facilities seem inevitably to bring in their wake a great deal of concern on the part of both the lay and medical communities. Relatively little attention, however, is given to what may be the largest single worldwide source of effectively carcinogenic ionizing radiation: tobacco. The risk of cancer deaths from the Chernobyl disaster are tobacco smoke is discussed.

  18. Alkali ionization detector

    DOEpatents

    Hrizo, John (Monroeville, PA); Bauerle, James E. (Plum Borough, PA); Witkowski, Robert E. (West Mifflin, PA)

    1982-01-01

    A calibration filament containing a sodium-bearing compound is included in combination with the sensing filament and ion collector plate of a sodium ionization detector to permit periodic generation of sodium atoms for the in-situ calibration of the detector.

  19. Application of thermal ionization mass spectrometry to investigations of molybdenum absorption in humans

    Microsoft Academic Search

    A. Giussani; Ch Hansen; F. Nüsslin; E. Werner

    1995-01-01

    Thermal ionization mass spectrometry (TIMS) has been developed for the detection of Mo in biological samples in order to enable investigations on absorption and biokinetics in humans. A double rhenium filament technique is employed for sample evaporation and ionization, coupled with a quadrupole filter. The negative MoO3 ions that are produced are then collected on a secondary electron multiplier and

  20. 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

  1. Modulated voltage metastable ionization detector

    NASA Technical Reports Server (NTRS)

    Carle, G. C.; Kojiro, D. R.; Humphrey, D. E. (inventors)

    1985-01-01

    The output current from a metastable ionization detector (MID) is applied to a modulation voltage circuit. An adjustment is made to balance out the background current, and an output current, above background, is applied to an input of a strip chart recorder. For low level concentrations, i.e., low detected output current, the ionization potential will be at a maximum and the metastable ionization detector will operate at its most sensitive level. When the detected current from the metastable ionization detector increases above a predetermined threshold level, a voltage control circuit is activated which turns on a high voltage transistor which acts to reduce the ionization potential. The ionization potential applied to the metastable ionization detector is then varied so as to maintain the detected signal level constant. The variation in ionization potential is now related to the concentration of the constituent and a representative amplitude is applied to another input of said strip chart recorder.

  2. 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.

  3. Resonant laser ionization of radioactive atoms*1

    NASA Astrophysics Data System (ADS)

    Köster, U.; Fedoseyev, V. N.; Mishin, V. I.

    2003-06-01

    Intense radioactive ion beams are produced by the isotope separation on-line method. The resonance ionization laser ion source (RILIS) can provide the chemical selectivity to separate beams with reduced isobaric contamination. The hot cavity RILIS at ISOLDE (CERN) uses copper vapor laser pumped dye lasers for the resonant transitions. Up to now 22 elements have been ionized with efficiencies of the order of 10%. Additional elements have been ionized with similar RILIS set-ups at the Institute of Spectroscopy (Troitsk), IRIS (Gatchina), Mainz University and TIARA (Takasaki). Ideas are discussed for future developments of this type of RILIS, which could further improve the efficiency, selectivity, rapidity of release and stability of the operation. The RILIS can also be applied for atomic spectroscopy studies of exotic radioactive isotopes, which are produced at rates of few atoms per second only. An interesting parallel is shown to the atomic vapor laser isotope separation (AVLIS), a large-scale application of resonance ionization, which could be used for the isotope enrichment of macroscopic amounts: tens of kg per h.

  4. 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.

  5. Desorption electrospray ionization mass spectrometry of intact bacteria

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  6. The negative ion states of sulfur hexafluoride

    NASA Astrophysics Data System (ADS)

    Chen, Edward C. M.; Shuie, Lih-Ren; Desai D'sa, Ela; Batten, C. F.; Wentworth, W. E.

    1988-04-01

    The reaction of SF6 with thermal electrons has been studied in a Ni-63 atmospheric pressure ionization source for a quadrupole mass spectrometer (API/MS). The major ions that are observed are the parent negative ion (SF-6) and the parent minus a fluorine atom (SF-5). The ratio of [SF-5]/[SF-6] is highly temperature dependent above 500 K. The dissociation energy of the ground state negative ion into SF-5 and F has been determined to be 1.35±0.1 eV. This gives values of 3.8±0.15 eV for the electron affinity of SF5 and 1.15±0.15 eV for the electron affinity of SF6. The negative ion states of sulfur hexafluoride have been described by ``pseudo-two-dimensional'' Morse potentials calculated using experimental data.

  7. 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…

  8. High brilliance negative ion and neutral beam source

    DOEpatents

    Compton, Robert N. (Oak Ridge, TN)

    1991-01-01

    A high brilliance mass selected (Z-selected) negative ion and neutral beam source having good energy resolution. The source is based upon laser resonance ionization of atoms or molecules in a small gaseous medium followed by charge exchange through an alkali oven. The source is capable of producing microampere beams of an extremely wide variety of negative ions, and milliampere beams when operated in the pulsed mode.

  9. Oscillations in Ionized Gases

    Microsoft Academic Search

    Lewi Tonks; Irving Langmuir

    1929-01-01

    A simple theory of electronic and ionic oscillations in an ionized gas has been developed. The electronic oscillations are so rapid (ca. 109 cycles) that the heavier positive ions are unaffected. They have a natural frequency nue=(ne2pim)12 and, except for secondary factors, do not transmit energy. The ionic oscillations are so slow that the electron density has its equilibrium value

  10. 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.

  11. Hysteresis of ionization waves

    SciTech Connect

    Dinklage, A. [Max-Planck-Institut fuer Plasmaphysik, EURATOM-Association, Wendelsteinstr. 1, 17491 Greifswald (Germany); Bruhn, B.; Testrich, H. [Institut fuer Physik, E.-M.-Arndt Universitaet Greifswald, Felix-Hausdorff-Str. 6, 17487 Greifswald (Germany); Wilke, C. [Leibniz-Institut fuer Plasmaforschung und Technologie, Felix-Hausdorff-Str. 2, 17489 Greifswald (Germany)

    2008-06-15

    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.

  12. Negative streamer development in FEP teflon

    NASA Technical Reports Server (NTRS)

    Beers, B. L.; Pine, V. W.; Hwang, H. C.; Bloomberg, H. W.

    1979-01-01

    A computational model is developed which describes the evolution and propagation of an ionizing front (negative streamer) in solid materials. The ionization front consists of drifting avalanching electrons moving self-consistently under the influence of their own space-charge field together with an applied external field. The required input information for the model consists of the functional dependence of the macroscopic transport coefficients on the local electric field, the initial conditions for beginning the calculation, and the strength of the applied field. A computational approach for specifying the transport coefficients and initional conditions is also described. The approach has been implemented by constructing three computer codes which sequentially interface, beginning with single electron scattering, and ending with streamer development. Computational results are presented for model calculations in Teflon. The overall model is perceived to provide a picture of the initiation phase of a propagating discharge in electron-irradiated dielectrics.

  13. Ionization of Trimethylgallium

    NASA Astrophysics Data System (ADS)

    Jiao Dejoseph, C. Q., Jr.; Garscadden, A.

    1999-10-01

    We report the cross sections for ionization of Trimethylgallium (GaC_3H_9) by electron impact and rates for gas-phase ion-molecule collisions, measured by Fourier transform mass spectrometry. Electron impact ionization of GaC_3H9 over the energy range of 10-70 eV produces the molecular ion and 7 fragment ions, with a total cross section of 1.1±0.1x10-15 cm^2 at 50 eV, and approximately constant to 70 eV. Absolute cross sections are determined by adding Ar to the gas sample for signal comparison with the known Ar ionization cross section. All of the observed ions contain Ga, and more than 97% of the ion population consists of GaC_2H_6^+, Ga^+ and GaCH_3^+ within the energy range studied. The results illustrate the preferential methyl abstractions. Gas-phase ion-molecule collisions in the 10-7 Torr\\cdots range produce GaC_2H_6^+ and Ga^+ at the expense of other ionic species. Ar^+ is found to react with GaC_3H9 also forming mainly GaC_2H_6^+ and Ga^+. No significant clustering reactions have been observed, implying that gas-phase ionic polymerization does not contribute to the Ga film formation.

  14. Ionization and equation of state of dense xenon at high pressures and high temperatures.

    PubMed

    Chen, Q F; Cai, L C; Gu, Y J; Gu, Y

    2009-01-01

    The ionization degree and equation of state of dense xenon plasma were calculated by using self-consistent fluid variational theory for temperature of 4-30kK and density of 0.01-8.5gcm;{3} . The dense fluid xenon will be ionized at high pressures and temperatures. The ionization energy of xenon will be lowered due to the interactions among all particles of Xe, Xe+ , Xe2+ , and e . The ionization degree is obtained from nonideal ionization equilibrium, taking into account the correlative contributions to the chemical potential which is determined self-consistently by the free energy function. The composition of xenon has been calculated with given densities and temperatures in the region of partial ionization. The calculated results show a pressure softening regime at the onset of ionization. Comparison is performed with available shock-wave experiments and other theoretical calculations. PMID:19257150

  15. Direct Analysis of Large Living Organism by Megavolt Electrostatic Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Ng, Kwan-Ming; Tang, Ho-Wai; Man, Sin-Heng; Mak, Pui-Yuk; Choi, Yi-Ching; Wong, Melody Yee-Man

    2014-09-01

    A new ambient ionization method allowing the direct chemical analysis of living human body by mass spectrometry (MS) was developed. This MS method, namely Megavolt Electrostatic Ionization Mass Spectrometry, is based on electrostatic charging of a living individual to megavolt (MV) potential, illicit drugs, and explosives on skin/glove, flammable solvent on cloth/tissue paper, and volatile food substances in breath were readily ionized and detected by a mass spectrometer.

  16. 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

  17. Analysis of solvent dyes in refined petroleum products by electrospray ionization mass spectrometry

    USGS Publications Warehouse

    Rostad, C.E.

    2010-01-01

    Solvent dyes are used to color refined petroleum products to enable differentiation between gasoline, diesel, and jet fuels. Analysis for these dyes in the hydrocarbon product is difficult due to their very low concentrations in such a complex matrix. Flow injection analysis/electrospray ionization/mass spectrometry in both negative and positive mode was used to optimize ionization of ten typical solvent dyes. Samples of hydrocarbon product were analyzed under similar conditions. Positive electrospray ionization produced very complex spectra, which were not suitably specific for targeting only the dyes. Negative electrospray ionization produced simple spectra because aliphatic and aromatic moieties were not ionized. This enabled screening for a target dye in samples of hydrocarbon product from a spill.

  18. Alignment-dependent ionization of H2+: From multiphoton ionization to tunneling ionization

    NASA Astrophysics Data System (ADS)

    Zhang, Bin; Yuan, Jianmin; Zhao, Zengxiu

    2012-03-01

    We investigate the strong-field ionization for the ground state of H2+ by numerically solving the three-dimensional (3D) time-dependent Schrödinger equation (TDSE), and comparisons have been made among the TDSE, the different versions of molecular strong-field approximation (MO-SFA) and the molecular Ammosov-Delone-Krainov (MO-ADK) approximation. The study shows that, for the TDSE results, the ratio of ionization rates between perpendicular and parallel alignments displays a step-like structure against the Keldysh parameter ?. For small internuclear distances, the transition between the steps are found to be around ??1 and is recognized as the competition between the multiphoton ionization (MPI) and tunneling ionization (TI). The ionization is more isotropic in the MPI regime. For large internuclear distances, the transition position shifts to larger ? due to the charge-resonance-enhanced ionization (CREI). Different versions of strong-field ionization theories are compared against the TDSE results.

  19. Negative acoustic index metamaterial

    NASA Astrophysics Data System (ADS)

    Fok, L.; Zhang, X.

    2011-06-01

    Acoustic metamaterials utilizing periodic deep subwavelength resonators can attain negative acoustic properties unavailable in nature. We have developed a negative acoustic index metamaterial for water that combines Helmholtz and rod-spring resonators to control effective bulk modulus and mass density, respectively. Effective properties extracted from full-wave simulations of our metamaterial show that negative real components of bulk modulus and density occur simultaneously, resulting in a negative real component of the acoustic index. Experimental measurements on a sample of this metamaterial confirm that the real components of the acoustic index and bulk modulus attain negative values, but the density does not become negative. The primary causes of this are identified and potential solutions are presented.

  20. NEGATIVE SYMPTOMS IN DEPRESSION

    PubMed Central

    Chaturvedi, Santosh K.; Sarmukaddam, Sanjeev

    1985-01-01

    SUMMARY Negative symptoms have been assessed in 34 cases of major depression (ROC) using the scale for assessment of negative symptoms. Negative symptoms were found to be quite frequently observed in these cases; common negative symptoms were inability to enjoy recreational interests and activities (76%), feelings of anhedonia (64.7%) and physical anergia (55.9%). Poverty of speech was found to be more in younger patients (P < .001). Avolition was seen more frequently in unmarried (P < .05) patients. No other signiticant correlation was noticed between demographic variables and negative symptoms. The implications of evaluating negative symptoms systematically in depressives are for future research especially for prognostication, treatment responses and classification of depression based on such symptoms. PMID:21927088

  1. Thermal ionization ion mobility spectrometry of alkali salts.

    PubMed

    Tabrizchi, Mahmoud

    2003-07-01

    Positive and negative thermal ionization ion mobility spectra (TI-IMS) of some sodium and potassium halides are reported here. The data provide the first measurement of the thermal ionization ion mobility spectrometry of inorganic compounds. A thin Nichrome filament was used as a thermionic ionization source. Sample was directly deposited on the filament, where it was heated and ionized. Each salt produced a different ion mobility pattern, but all sodium salts spectra were common in their first peak. This peak differs from the common peak observed in the spectra of potassium salts. The drift time of the second peak in all spectra was found to be linearly dependent on the size of the counteranion of the salt. Negative thermal ionization ion mobility spectra of alkali halides were also observed. An alkali halide salt (MX), in general, produced its own anion as well as some heavier ions that are thought to be hydrated X- (MX)n species. The capability of the method in quantitative analysis was demonstrated by measuring potassium impurity in sodium bromide. A detection limit of 0.01% K+ in NaBr and a linear rage of 3 orders of magnitude were obtained. The results from this study suggest that TI-IMS has potential as a field technique for the detection of some elements in samples. PMID:12964757

  2. 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.

  3. Negative ion density fronts

    NASA Astrophysics Data System (ADS)

    Kaganovich, Igor

    2001-05-01

    Negative ions tend to stratify in electronegative plasmas with hot electrons (electron temperature Te much larger than ion temperature Ti, Te?Ti). The boundary separating a plasma containing negative ions, and a plasma without negative ions, is usually thin so that the negative ion density falls rapidly to zero—forming a negative ion density front. Theoretical, experimental, and numerical results giving the spatio-temporal evolution of negative ion density fronts during plasma ignition, the steady state, and extinction (afterglow) are reviewed. 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 the analysis of plasma density profile evolution in strongly nonisothermal plasmas.

  4. Surface Ionization Type Ion Source of Ba+ Ions for Use in Collision Experiments

    Microsoft Academic Search

    R. K. Feeney; F. M. Bacon; M. T. Elford; J. W. Hooper

    1972-01-01

    A surface ionization type ion source, which produces a Ba+ ion beam of known chemical purity and excitation state, has been developed specifically for use in collision experiments. Barium vapor is surface ionized on a rhenium filament that is heated to approximately 1800°C by the passage of a direct current. The water cooled source provides ion currents of about 10

  5. 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

  6. Isomer discrimination of polycyclic aromatic hydrocarbons in the Murchison meteorite by resonant ionization

    E-print Network

    de Vries, Mattanjah S.

    Isomer discrimination of polycyclic aromatic hydrocarbons in the Murchison meteorite by resonant;Abstract We have used two-color resonant two-photon ionization (2C-R2PI) mass spectrometry to discriminate demonstrated isomer discrimination of PAHs by chemical ionization mass spectrometry with carbon dioxide

  7. Neon and Argon optical emission lines in ionized gaseous nebulae: Implications and applications

    E-print Network

    Enrique Perez-Montero; Guillermo F. Hagele; Thierry Contini; Angeles I. Diaz

    2007-07-18

    In this work we present a study of the strong optical collisional emission lines of Ne and Ar in an heterogeneous sample of ionized gaseous nebulae for which it is possible to derive directly the electron temperature and hence the chemical abundances of neon and argon. We calculate using a grid of photoionization models new ionization correction factors for these two elements and we study the behaviour of Ne/O and Ar/O abundance ratios with metallicity. We find a constant value for Ne/O, while there seems to be some evidence for the existence of negative radial gradients of Ar/O over the disks of some nearby spirals. We study the relation between the intensities of the emission lines of [NeIII] at 3869 \\AA and [OIII] at 4959 \\AA and 5007 \\AA. This relation can be used in empirical calibrations and diagnostic ratios extending their applicability to bluer wavelengths and therefore to samples of objects at higher redshifts. Finally, we propose a new diagnostic using [OII], [NeIII] and Hdelta emission lines to derive metallicities for galaxies at high z.

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

    DOEpatents

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

    2013-02-26

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

  9. Positron impact ionization phenomena

    NASA Astrophysics Data System (ADS)

    Murtagh, Daniel James

    In the present work, a beam of positrons, obtained from a radioactive source (MNa) in conjunction with a W moderator and guided by a magnetic field, has been used to investigate low energy positron-impact ionization phenomena from atomic and molecular targets. For He below threshold, the investigation discovered vacuum contaminants in creased with gas load and hence concluded that the high 7-ray/ion signal observed by Szluinska and Laricchia (2004a) in Ne could not be safely attributed to annihila tion. A detailed measurement of the total ionization cross-section for He has been performed from below threshold for Ps formation to high energy. Combined with previously measured data and previously measured direct ionization cross-sections (Moxom et al 1996, Ashley et al 1996), a new determination of the positronium formation cross-section has been achieved and compared to other available experi mental measurements and theoretical calculations. Measurements of the excited state (n > 1) positronium formation cross-section for He and Ar have been performed and compared to available theoretical calcu lations. This work has been motivated both for a direct comparison with theory and to test the hypothesis that structure observed in the total (all n) positron ium formation cross-sections for the heavier noble gases, is due to excited state positronium formation (Laricchia et al 2002). The present study is unable to verify fully this hypothesis due to the experimental methods insensitivity to positronium formation in to the 2S or n > 2 states. However, the present results are close to the most sophisticated theoretical calculation of positronium formation into the 2P state (Campbell et al 1998).

  10. Resonance ionization detection of combustion radicals

    SciTech Connect

    Cool, T.A. [Cornell Univ., Ithaca, NY (United States)

    1993-12-01

    Fundamental research on the combustion of halogenated organic compounds with emphasis on reaction pathways leading to the formation of chlorinated aromatic compounds and the development of continuous emission monitoring methods will assist in DOE efforts in the management and disposal of hazardous chemical wastes. Selective laser ionization techniques are used in this laboratory for the measurement of concentration profiles of radical intermediates in the combustion of chlorinated hydrocarbon flames. A new ultrasensitive detection technique, made possible with the advent of tunable VUV laser sources, enables the selective near-threshold photoionization of all radical intermediates in premixed hydrocarbon and chlorinated hydrocarbon flames.

  11. A surface ionization source

    E-print Network

    Buzatu, Daniel J.

    1995-01-01

    The Einzel Lens. 2 The Quadrupole Triplet . . 3. The Beam Scanner. . . 4 The Four-plate Detectors and Faraday Cups. III TESTING AND OPTIMIZING THE BEAM LINE 10 12 13 A. Initial Results. IV THE THEORY OF SURFACE IONIZATION . . . . . V ION SOURCES. 21... representation of the beam line. Page 2 Schematic of the vacuum system 3 Cross section of the einzel lens, with equipotentials. 4 The quadrupole triplet . 5 Polanties of the quadrupole tnplet 6 Beam scanner probe with V-shaped vane for x, y sensing...

  12. Reactive accelerated cluster erosion (RACE) by ionized cluster beams

    NASA Astrophysics Data System (ADS)

    Gspann, Jürgen

    1996-05-01

    Beams of ionized clusters accelerated up to about 120 keV kinetic energy per cluster are used for cluster impact lithography. Chemical reactions of clusters of CO 2, or of SF 6, respectively, are found to assist the physical erosion by hypervelocity cluster impacts in yielding volatile products. Natural diamond, silicon and Pyrex glass have been microstructured showing very smooth eroded surfaces.

  13. HIGH-SENSITIVITY THERMOSPRAY IONIZATION MASS SPECTROMETRY OF DYES

    EPA Science Inventory

    A series of dyes belonging to different chemical classes have been analyzed by thermospray (TSP) ionization mass spectrometry using a modified source containing a wire-repeller. etection limits were determined and found to be in the range 0.05-20ng, which are lower by a factor of...

  14. 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.…

  15. Positive and negative perfectionism

    Microsoft Academic Search

    L. A. Terry-Short; R. Glynn Owens; P. D. Slade; M. E. Dewey

    1995-01-01

    Previous research into perfectionism has focused on clinical populations resulting in a bias towards a negativistic, pathologically inclined conceptualization. The present study investigated the possibility of distinguishing aspects of perfectionism on the basis of perceived consequences, mirroring a behavioural distinction between positive and negative reinforcement. A 40-item questionnaire, designed to measure perfectionism defined in terms of both positive and negative

  16. Communicating with Negative People

    Microsoft Academic Search

    Adriana Vintean

    2007-01-01

    We all must have been negative at work at one time or another and most of us didn't like to be that way. For some people it is a way of being. Some people seem to flourish in a negative atmosphere. Often people defend their right to be nasty as their legitimate duty. Do Emergency Communications Centers have an over-abundance

  17. Ontological Metaphors for Negative Energy in an Interdisciplinary Context

    ERIC Educational Resources Information Center

    Dreyfus, Benjamin W.; Geller, Benjamin D.; Gouvea, Julia; Sawtelle, Vashti; Turpen, Chandra; Redish, Edward F.

    2014-01-01

    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…

  18. Capillary atmospheric pressure electron capture ionization (cAPECI): a highly efficient ionization method for nitroaromatic compounds.

    PubMed

    Derpmann, Valerie; Mueller, David; Bejan, Iustinian; Sonderfeld, Hannah; Wilberscheid, Sonja; Koppmann, Ralf; Brockmann, Klaus J; Benter, Thorsten

    2014-03-01

    We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O2(-) or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O2(-) leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry. PMID:24399666

  19. Capillary Atmospheric Pressure Electron Capture Ionization (cAPECI): A Highly Efficient Ionization Method for Nitroaromatic Compounds

    NASA Astrophysics Data System (ADS)

    Derpmann, Valerie; Mueller, David; Bejan, Iustinian; Sonderfeld, Hannah; Wilberscheid, Sonja; Koppmann, Ralf; Brockmann, Klaus J.; Benter, Thorsten

    2014-03-01

    We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O2 - or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O2 - leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry.

  20. Miniaturized gas ionization sensors using carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Modi, Ashish; Koratkar, Nikhil; Lass, Eric; Wei, Bingqing; Ajayan, Pulickel M.

    2003-07-01

    Gas sensors operate by a variety of fundamentally different mechanisms. Ionization sensors work by fingerprinting the ionization characteristics of distinct gases, but they are limited by their huge, bulky architecture, high power consumption and risky high-voltage operation. Here we report the fabrication and successful testing of ionization microsensors featuring the electrical breakdown of a range of gases and gas mixtures at carbon nanotube tips. The sharp tips of nanotubes generate very high electric fields at relatively low voltages, lowering breakdown voltages several-fold in comparison to traditional electrodes, and thereby enabling compact, battery-powered and safe operation of such sensors. The sensors show good sensitivity and selectivity, and are unaffected by extraneous factors such as temperature, humidity, and gas flow. As such, the devices offer several practical advantages over previously reported nanotube sensor systems. The simple, low-cost, sensors described here could be deployed for a variety of applications, such as environmental monitoring, sensing in chemical processing plants, and gas detection for counter-terrorism.

  1. Electron ionization of cyclohexene

    NASA Astrophysics Data System (ADS)

    Jiao, C. Q.; Adams, S. F.

    2014-11-01

    The absolute total cross section of electron ionization on cyclohexene (CHE) and the branching ratios of the product ions are measured in an electron energy range of 10–200 eV. The total cross section reaches a maximum of 1.5 × 10?15 cm2 at 80 eV. Sixteen noteworthy product ions are observed from the ionization of CHE that have partial cross sections greater than 5 × 10?18 cm2 at 50 eV: C2H3+, C3H3,5+, C4H2–7+, C5H5–7+, and C6H5,7,9,10+, where branching ratios are reported for each. The most abundant ions within the electron energy range studied are the parent ion C6H10+ and fragment ions C5H7+ and C4H6+, with combined abundance accounting more than half of the ion population. The reaction pathways forming certain fragment ions at energies near their thresholds are discussed.

  2. Femtosecond laser ionization of organic amines with very low ionization potentials: relatively small suppressed ionization features.

    PubMed

    Yatsuhashi, Tomoyuki; Obayashi, Takashi; Tanaka, Michinori; Murakami, Masanao; Nakashima, Nobuaki

    2006-06-29

    We examined the femtosecond nonresonant ionization of organic amines with vertical ionization potentials as low as 5.95 eV. The quantitative evaluation of suppressed ionization relative to the single active electron approximation model was done by comparing the saturation intensity, I(sat), in experiments and theory. ADK theory was found to be useful in predicting the ionization yield in the I(sat) scale within a factor of 2, even for molecules with very low ionization potentials. The degree of suppression was, however, smaller than that of benzene. The localization of electrons on the nitrogen atom was found to affect the ionization behavior under the strong laser field. The delocalized pi electrons in benzene could not follow the laser field adiabatically, while those in localized molecular orbitals could. In addition, the growth of a tunneling barrier due to the screening effect in amines may be relatively smaller than that in benzene. PMID:16789760

  3. Theory of negative corona in oxygen

    NASA Astrophysics Data System (ADS)

    Morrow, R.

    1985-09-01

    Theoretical predictions are given of the development of the current and the distributions of charge and electric field in negative corona, or Trichel current pulses [G. W. Trichel, Phys. Rev. 54, 1078 (1938)], in oxygen at a pressure of 6.67 kPa (50 Torr). For a 10-mm-diam negative sphere located 20 mm from a positive plane, the calculated current pulse has a rise time of 11 ns, a pulse width of 50 ns, and a peak amplitude of 13 mA. These results agree satisfactorily with experimental values. The predicted velocity of the cathode-directed light pulse also agrees well with observations. The theory is based on the accurate numerical solution of Poisson's equation in conjunction with the continuity equations for electrons, positive ions, and negative ions. The effects of ionization, attachment, recombination, electron diffusion, and photoemission and ion secondary-electron emission from the cathode are all included. The initial steep rise of the current pulse is largely due to rapid ionization and electron motion in the high Laplacian field near the cathode. As the discharge develops, a dense plasma forms near the cathode, leading to strong space-charge distortion of the field. A prominent cathode fall region is formed immediately adjacent to the cathode, an almost zero field is formed within the plasma and the field is enhanced over the region to the anode. The current pulse is quenched because the low electric field in the plasma immobilizes the majority of the electrons which then undergo three-body attachment; furthermore, the cathode fall region becomes reduced to such a short distance that insignificant current is produced from this region. Because of the low mobility of the negative ions, the current remains low and the structure of the space-charge fields changes only slowly with time between pulses.

  4. Ionization photophysics and spectroscopy of cyanoacetylene

    SciTech Connect

    Leach, Sydney; Champion, Norbert [LERMA UMR CNRS 8112, Observatoire de Paris-Meudon, 5 place Jules-Jansen, 92195 Meudon (France)] [LERMA UMR CNRS 8112, Observatoire de Paris-Meudon, 5 place Jules-Jansen, 92195 Meudon (France); Garcia, Gustavo A.; Fray, Nicolas; Gaie-Levrel, François [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, B.P. 48, 91192, Gif-sur-Yvette Cedex (France)] [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, B.P. 48, 91192, Gif-sur-Yvette Cedex (France); Mahjoub, Ahmed; Bénilan, Yves; Gazeau, Marie-Claire; Schwell, Martin [LISA UMR CNRS 7583, Université Paris Est Créteil and Université Paris Diderot, Institut Pierre Simon Laplace, 61 Avenue du Général de Gaulle, 94010 Créteil (France)] [LISA UMR CNRS 7583, Université Paris Est Créteil and Université Paris Diderot, Institut Pierre Simon Laplace, 61 Avenue du Général de Gaulle, 94010 Créteil (France)

    2014-05-07

    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 HC{sub 3}N involves new aspects and new assignments of the vibrational components to excitation of the A{sup 2}?{sup +} and B{sup 2}? 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 B{sup 2}? state of HC{sub 3}N{sup +}. A number of the measured TIY features are suggested to be vibrational components of Rydberg series converging to the C{sup 2}?{sup +} state of HC{sub 3}N{sup +} 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.

  5. Negative tandem mirror

    SciTech Connect

    Poulsen, P.; Allen, S.L.; Casper, T.A.; Grubb, D.P.; Jong, R.A.; Nexsen, W.E.; Porter, G.D.; Simonen, T.C.

    1981-11-30

    A tandem mirror configuration can be created by combining hot electron end cell plasmas with neutral beam pumping. A region of large negative potential formed in each end cell confines electrons in the central cell. The requirement of charge neutrality causes the central cell potential to become negative with respect to ground in order to confine ions as well as electrons. We discuss the method of producing and calculating the desired axial potential profile, and show the calculated axial potential profile and plasma parameters for a negative configuration of TMX-Upgrade.

  6. Kriging without negative weights

    SciTech Connect

    Szidarovszky, F.; Baafi, E.Y.; Kim, Y.C.

    1987-08-01

    Under a constant drift, the linear kriging estimator is considered as a weighted average of n available sample values. Kriging weights are determined such that the estimator is unbiased and optimal. To meet these requirements, negative kriging weights are sometimes found. Use of negative weights can produce negative block grades, which makes no practical sense. In some applications, all kriging weights may be required to be nonnegative. In this paper, a derivation of a set of nonlinear equations with the nonnegative constraint is presented. A numerical algorithm also is developed for the solution of the new set of kriging equations.

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

    PubMed

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

    2014-11-18

    We present laser desorption atmospheric pressure photochemical ionization mass spectrometry (LD/APPCI MS) for rapid throughput analysis of complex organic mixtures, without the need for matrix, electric discharge, secondary electrospray, or solvents/vaporizers. Analytes dried on a microscope slide are vaporized in transmission geometry by a laser beam aligned with the atmospheric pressure inlet of the mass spectrometer. The laser beam initiates a cascade of reactions in the region between the glass slide and MS inlet, leading to generation of reagent ions for chemical ionization of vaporized analyte. Positive analyte ions are generated predominantly by proton transfer, charge exchange, and hydride abstraction, whereas negative ions are generated by electron capture or proton transfer reactions, enabling simultaneous analysis of saturated, unsaturated, and heteroatom-containing hydrocarbons. The absence of matrix interference renders LD/APPCI MS particularly useful for analysis of small molecules (<2000 Da) such as those present in petroleum crude oil and petroleum deposits. [M + H](+) and M(+•) dominate the positive-ion mass spectra for olefins and polyaromatic hydrocarbons, whereas saturated hydrocarbons are observed mainly as [M - H](+) and/or M(+•). Heteroatom-containing hydrocarbons are observed predominantly as [M + H](+). [M - H](-) and M(-•) are the dominant negative ions observed for analytes of lower gas-phase basicity or higher electron affinity than O2. The source was coupled with a 9.4 T Fourier transform ion cyclotron resonance mass spectrometer (FTICR MS) to resolve and identify thousands of peaks from Athabasca bitumen heavy vacuum gas oil distillates (400-425 and 500-538 °C), enabling simultaneous characterization of their polar and nonpolar composition. We also applied LD/APPCI FTICR MS for rapid analysis of sodium and calcium naphthenate deposits with little to no sample pretreatment to provide mass spectral fingerprints that enable reliable compositional characterization. PMID:25347814

  8. 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.

  9. Logo and Negative Numbers.

    ERIC Educational Resources Information Center

    Strawn, Candace A.

    1998-01-01

    Describes LOGO's turtle graphics capabilities based on a sixth-grade classroom's activities with negative numbers and Logo programming. A sidebar explains LOGO and offers suggestions to teachers for using LOGO effectively. (LRW)

  10. Photoinduced Rydberg ionization spectroscopy

    NASA Astrophysics Data System (ADS)

    Taylor, David P.; Goode, Jon G.; LeClaire, Jeffrey E.; Johnson, Philip M.

    1995-10-01

    A new method for the high-resolution electronic spectroscopy of cations with mass resolution. Optical transitions from Rydberg states converging on the ground state of the cation to states with electronically excited cores are detected by their rapid autoionization. The spectrum of these transitions provide ionic information because the photoabsorption cross-section of a molecule in a high-n Rydberg state closely mirrors the spectrum of the ion core. The technique presented here, called photoinduced Rydberg ionization (PIRI) spectroscopy, is applied in this case to record the B˜ 2E2g?X˜ 2E1g transition of the benzene cation via the vibrational origin of the X˜ 2E1g ionic state.

  11. Ionizing radiation detector

    DOEpatents

    Thacker, Louis H. (Knoxville, TN)

    1990-01-01

    An ionizing radiation detector is provided which is based on the principle of analog electronic integration of radiation sensor currents in the sub-pico to nano ampere range between fixed voltage switching thresholds with automatic voltage reversal each time the appropriate threshold is reached. The thresholds are provided by a first NAND gate Schmitt trigger which is coupled with a second NAND gate Schmitt trigger operating in an alternate switching state from the first gate to turn either a visible or audible indicating device on and off in response to the gate switching rate which is indicative of the level of radiation being sensed. The detector can be configured as a small, personal radiation dosimeter which is simple to operate and responsive over a dynamic range of at least 0.01 to 1000 R/hr.

  12. Isotropic Single Negative Metamaterials

    Microsoft Academic Search

    Pavel PROTIVA; Michal BLÁHA; Ján ZEHENTNER

    This paper presents the application of simple, and therefore cheap, planar resonators for building 3D isotropic metamaterials. These resonators are: a broad- side-coupled split ring resonator with a magnetic response providing negative permeability; an electric dipole termi- nated by a loop inductor together with a double H-shaped resonator with an electric response providing negative permittivity. Two kinds of 3D isotropic

  13. Negative symptoms in schizophrenia.

    PubMed

    Boutros, Nash N; Mucci, Armida; Diwadkar, Vaibhav; Tandon, Rajiv

    2014-04-01

    Clinical heterogeneity is a confound common to all of schizophrenia research. Deficit schizophrenia has been proposed as a homogeneous disease entity within the schizophrenia syndrome. Utilizing the Schedule for the Deficit Syndrome (SDS) has allowed the definition of a subgroup dominated by persistent clusters of negative symptoms. While a number of studies have appeared over the years examining the electrophysiological correlates of the cluster of negative symptoms in schizophrenia, only a few studies have actually focused on the deficit syndrome (DS). PubMed as well as MEDLINE were searched for all reports indexed for "negative symptoms" or "deficit syndrome" and one of the following electrophysiology assessment tools: electroencephalography (EEG), evoked potentials (EPs), or polysomnography (PSG). While this line of research is evidently in its infancy, two significant trends emerge. First, spectral EEG studies link increased slow wave activity during wakefulness to the prevalence of negative symptoms. Secondly, sleep studies point to an association between decrease in slow wave sleep and prevalence of negative symptoms. Several studies also indicate a relationship of negative symptoms with reduced alpha activity. A host of other abnormalities--including sensory gating and P300 attenuation--are less consistently reported. Two studies specifically addressed electrophysiology of the DS. Both studies provided evidence suggesting that the DS may be a separate disease entity and not simply a severe form of schizophrenia. PMID:23428787

  14. Positive and negative gas-phase ion chemistry of chlorofluorocarbons in air at atmospheric pressure.

    PubMed

    Bosa, Elisabetta; Paradisi, Cristina; Scorrano, Gianfranco

    2003-01-01

    This paper presents a report on the ionization/dissociation of some representative chlorofluorocarbons (CFCs) induced by corona discharges in air at atmospheric pressure. Both positive and negative ions formed from Freons 1,1,1-trichlorotrifluoroethane (CFC 113a), 1,1,2-trichlorotrifluoroethane (CFC 113), and 1,1,1,2-tetrachlorodifluoroethane (CFC 112a) were analyzed using an atmospheric pressure chemical ionization mass spectrometry (APCI-MS) instrument. Energy-resolved mass spectra were obtained by modulating the kinetic energy of the ions via adjustment of the sampling cone potential (V(cone)). Positive ion spectra of the CFCs (M) at low V(cone) show no signals due to either M(+)* or MH(+) but only those due to species [M - Cl](+) and CX(3)(+) (X = Cl, F), likely formed via C-Cl and C-C bond cleavages following ionization via charge exchange. Charge localization in the products of C-C bond cleavage in M(+)* is driven by the stability of the neutral fragment. At low V(cone) the hydrates [M - Cl](+)(H(2)O) are also observed. In the case of 1,1,2,-trichlorotrifluoroethane, [M - F](+) species also form as a result of ion-molecule reactions. As V(cone) is increased collision-induced dissociation of [M - Cl](+) and [M - F](+), i.e., the perhalogenated cations C(2)X(5)(+) (X = Cl, F), takes place via carbene elimination. In some cases such elimination is preceded or accompanied by rearrangements involving transfer of halogen from one carbon to the other. Evidence is also presented for the occurrence of a condensation reaction of C(2)Cl(3)F(2)(+) with water to form a C(2)Cl(2)F(2)HO(+) species via elimination of HCl. Negative ion spectra are dominated by Cl(-) and its ion-neutral complexes with M and with water. Additional components of the plasma include ion-neutral complexes O(3)(-)(M), the molecular anion M(-) (observed only with 1,1,2-trichlorotrifluoroethane), and an interesting species corresponding to [M - Cl + O](-). The origin and structure of these [M - Cl + O](-) species are discussed in terms of available thermochemical and reactivity data and current mechanistic views concerning reaction of O(2)(-) with halogenated compounds. The observation of both positive and negative ions containing oxygen is of special relevance to development of new processes for the treatment of volatile organic compounds (VOCs) based on oxidative decomposition induced by corona discharges in air at room temperature and pressure. PMID:12478549

  15. Aliphatic Hydrocarbon Spectra by Helium Ionization Mass Spectrometry (HIMS) on a Modified Atmospheric-Pressure Source Designed for Electrospray Ionization

    NASA Astrophysics Data System (ADS)

    Yang, Zhihua; Attygalle, Athula B.

    2011-08-01

    Chemical-ionization techniques that use metastable species to ionize analytes traditionally use a flat pin or a sharp solid needle onto which the high potential needed to generate the discharge plasma is applied. We report here that direct analysis of samples containing volatile and semivolatile compounds, including saturated and unsaturated aliphatic hydrocarbons, can be achieved on any electrospray-ionization mass spectrometer by passing helium though the sample delivery metal capillary held at a high potential. In the helium plasma ionization source (HPIS) described here, the typical helium flow required (about 20-30 mL/min), was significantly lower than that needed for other helium-ionization sources. By this procedure, positive ions were generated by nominal hydride ion removal from molecules emanating from heated saturated hydrocarbons as large as tetratetracontane (C44H90), at capillary voltages ranging from 2.0 to 4.0 kV. Unsaturated hydrocarbons, on the other hand, underwent facile protonation under much lower capillary voltages (0.9 to 2.0 kV). Although saturated and monounsaturated hydrocarbons bearing the same number of carbon atoms generate ions of the same m/z ratio, a gas-phase deuterium exchange method is described to ascertain the identity of these isomeric ions originating from either protonation or hydride abstraction mechanisms. Moreover, mass spectrometric results obtained by exposing unsaturated hydrocarbons to D2O vapor in an HPIS-MS instrument confirmed that the proton donor for ionization of unsaturated hydrocarbons is protonated water.

  16. Separatory determination of diastereomeric ibuprofen glucuronides in human urine by liquid chromatography/electrospray ionization-mass spectrometry.

    PubMed

    Ikegawa, S; Murao, N; Oohashi, J; Goto, J

    1998-01-01

    A method for the separatory determination of diastereomeric isomers of glucuronic acid conjugates of ibuprofen having a carboxyl group at the chiral center by liquid chromatography (LC)/electrospray ionization (ESI)-mass spectrometry (MS) has been developed. The authentic specimens of acyl glucuronides of R(-)- and S(+)-ibuprofen were chemically synthesized by the Mitsunobu reaction. In the ESI mode, the glucuronides were characterized by an abundant quasi-molecular ion [M-H]-, and the formation of the negative ion was markedly influenced by a drift voltage. The resolution of diastereomeric isomers was achieved on a Develosil ODS-HG-5 column with 20 mM ammonium acetate (pH 5.0):acetonitrile (5:2, v/v) as a mobile phase where diastereomers were monitored with a corresponding quasi-molecular ion. After oral administration of racemic ibuprofen, a preferential excretion of (S)-ibuprofen glucuronide into the urine was observed. PMID:9861489

  17. 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.

  18. Spectral Evidence for Ionization in Air-Filled Glow Discharge Tubes: Application to Sprites

    NASA Astrophysics Data System (ADS)

    Armstrong, R. A.; Williams, E. R.; Golka, R. K.; Williams, D. R.

    2001-12-01

    The question of ionization in sprites and the evidence for VLF backscatter from sprites has motivated a quantitative spectral analysis of the various (classical) regions of the glow discharge tube under DC excitation and at air densities appropriate for sprites in the mesosphere. A PR-650 colorimeter (Photo Research, Inc.) has enabled calibrated irradiance measurements for localized zones along the axis of the discharge tube--in the dominantly blue negative glow, in the Faraday dark space and in the red/pink positive column. Consistent with historical nomenclature, nitrogen first and second positive emission is dominant in the positive column (associated with neutral N2), and nitrogen first negative emission, with a prominent peak at 4278 A, is dominant in the blue negative glow (associated with ionized N2+). Whereas nitrogen first and second positive emission are also detected in the negative glow, no spectral evidence for ionization (no 4279, no 3914, no Meinel) is found in the red/pink positive column. This negative result is attributed not to an absence of ionization in the positive column, but rather to a sparse population of N2+ relative to neutral nitrogen in this region, and to the prominent emission in the blue part of the spectrum due to nitrogen second positive. A similar interpretation may be appropriate for the time-integrated spectra from the red body of sprites, also lacking direct evidence for ionization.

  19. High pressure xenon ionization detector

    DOEpatents

    Markey, John K. (New Haven, CT)

    1989-01-01

    A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0.degree. to 30.degree. C.

  20. High pressure xenon ionization detector

    DOEpatents

    Markey, J.K.

    1989-11-14

    A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0 to 30 C. 2 figs.

  1. Pulsed helium ionization detection system

    DOEpatents

    Ramsey, Roswitha S. (Knoxville, TN); Todd, Richard A. (Knoxville, TN)

    1987-01-01

    A helium ionization detection system is provided which produces stable operation of a conventional helium ionization detector while providing improved sensitivity and linearity. Stability is improved by applying pulsed dc supply voltage across the ionization detector, thereby modifying the sampling of the detectors output current. A unique pulse generator is used to supply pulsed dc to the detector which has variable width and interval adjust features that allows up to 500 V to be applied in pulse widths ranging from about 150 nsec to about dc conditions.

  2. Pulsed helium ionization detection system

    DOEpatents

    Ramsey, R.S.; Todd, R.A.

    1985-04-09

    A helium ionization detection system is provided which produces stable operation of a conventional helium ionization detector while providing improved sensitivity and linearity. Stability is improved by applying pulsed dc supply voltage across the ionization detector, thereby modifying the sampling of the detectors output current. A unique pulse generator is used to supply pulsed dc to the detector which has variable width and interval adjust features that allows up to 500 V to be applied in pulse widths ranging from about 150 nsec to about dc conditions.

  3. 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.

  4. Mechanistic investigation of ionization suppression in electrospray ionization

    Microsoft Academic Search

    Richard King; Ryan Bonfiglio; Carmen Fernandez-Metzler; Cynthia Miller-Stein; Timothy Olah

    2000-01-01

    We show results from experiments designed to determine the relative importance of gas phase processes and solution phase processes\\u000a into ionization suppression observed in biological sample extracts. The data indicate that gas phase reactions leading to\\u000a the loss of net charge on the analyte is not likely to be the most important process involved in ionization suppression. The\\u000a results point

  5. 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.

  6. Equation of state of partially ionized argon plasma

    SciTech Connect

    Chen, Q. F.; Zheng, J.; Gu, Y. J.; Chen, Y. L.; Cai, L. C.

    2011-11-15

    The ionization degree, Hugoniots, and equation of state of partially ionized argon plasma were calculated by using self-consistent fluid variational theory for temperature of 6-50 kK and density of 0.05-4.0 g/cm{sup 3}. The corrections of lowering of ionization energy of fluid argon caused by the interactions among all particles of Ar, Ar{sup +}, Ar{sup 2+}, and e have been taken into consideration in terms of the correlation contributions to the chemical potential which is determined self-consistently by the free energy function. The initial density effects of gas argon under shock compression have been discussed. Comparison is performed with available shock-wave experiments and other theoretical calculations.

  7. Negative Electron Affinity Mechanism for Diamond Surfaces

    NASA Technical Reports Server (NTRS)

    Krainsky, I. L.; Asnin, V. M.

    1998-01-01

    The energy distribution of the secondary electrons for chemical vacuum deposited diamond films with Negative Electron Affinity (NEA) was investigated. It was found that while for completely hydrogenated diamond surfaces the negative electron affinity peak in the energy spectrum of the secondary electrons is present for any energy of the primary electrons, for partially hydrogenated diamond surfaces there is a critical energy above which the peak is present in the spectrum. This critical energy increases sharply when hydrogen coverage of the diamond surface diminishes. This effect was explained by the change of the NEA from the true type for the completely hydrogenated surface to the effective type for the partially hydrogenated surfaces.

  8. Trace detection of inorganic oxidants using desorption electrospray ionization (DESI) mass spectrometry

    Microsoft Academic Search

    Ewa Sokol; Ayanna U. Jackson; R. Graham Cooks

    2011-01-01

    Desorption electrospray ionization (DESI), an established ambient ionization method in mass spectrometry (MS) for the analysis\\u000a of organic compounds, is applied here to trace detection of inorganic salts, including inorganic oxidants. In-situ surface\\u000a analysis of targeted compounds, including nitrogen-, halogen- and sulfur-salts, down to sub-nanogram levels, was performed\\u000a using DESI-MS. Successful experiments were carried out in both the negative and

  9. Measurement of laser activated electron tunneling from semiconductor zinc oxide to adsorbed organic molecules by a matrix assisted laser desorption ionization mass spectrometer.

    PubMed

    Zhong, Hongying; Fu, Jieying; Wang, Xiaoli; Zheng, Shi

    2012-06-01

    Measurement of light induced heterogeneous electron transfer is important for understanding of fundamental processes involved in chemistry, physics and biology, which is still challenging by current techniques. Laser activated electron tunneling (LAET) from semiconductor metal oxides was observed and characterized by a MALDI (matrix assisted laser desorption ionization) mass spectrometer in this work. Nanoparticles of ZnO were placed on a MALDI sample plate. Free fatty acids and derivatives were used as models of organic compounds and directly deposited on the surface of ZnO nanoparticles. Irradiation of UV laser (?=355 nm) with energy more than the band gap of ZnO produces ions that can be detected in negative mode. When TiO(2) nanoparticles with similar band gap but much lower electron mobility were used, these ions were not observed unless the voltage on the sample plate was increased. The experimental results indicate that laser induced electron tunneling is dependent on the electron mobility and the strength of the electric field. Capture of low energy electrons by charge-deficient atoms of adsorbed organic molecules causes unpaired electron-directed cleavages of chemical bonds in a nonergodic pathway. In positive detection mode, electron tunneling cannot be observed due to the reverse moving direction of electrons. It should be able to expect that laser desorption ionization mass spectrometry is a new technique capable of probing the dynamics of electron tunneling. LAET offers advantages as a new ionization dissociation method for mass spectrometry. PMID:22595432

  10. 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 ...

  11. Study of electrochemical reactions using nanospray desorption electrospray ionization mass spectrometry.

    PubMed

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

    2012-07-01

    The combination of electrochemistry (EC) and mass spectrometry (MS) is a powerful analytical tool for studying mechanisms of redox reactions, identification of products and intermediates, and online derivatization/recognition of analytes. This work reports a new coupling interface for EC/MS by employing nanospray desorption electrospray ionization, a recently developed ambient ionization method. We demonstrate online coupling of nanospray desorption electrospray ionization MS with a traditional electrochemical flow cell, in which the electrolyzed solution emanating from the cell is ionized by nanospray desorption electrospray ionization for MS analysis. Furthermore, we show first coupling of nanospray desorption electrospray ionization MS with an interdigitated array (IDA) electrode enabling chemical analysis of electrolyzed samples directly from electrode surfaces. Because of its inherent sensitivity, nanospray desorption electrospray ionization enables chemical analysis of small volumes and concentrations of sample solution. Specifically, good-quality signal of dopamine and its oxidized form, dopamine o-quinone, was obtained using 10 ?L of 1 ?M solution of dopamine on the IDA. Oxidation of dopamine, reduction of benzodiazepines, and electrochemical derivatization of thiol groups were used to demonstrate the performance of the technique. Our results show the potential of nanospray desorption electrospray ionization as a novel interface for electrochemical mass spectrometry research. PMID:22720719

  12. Volumetric single negative metamaterials

    Microsoft Academic Search

    J. Zehentner; J. Machac

    This paper presents the results of a study of bulk single negative isotropic metamaterials. Magnetic and electric metamaterials are treated separately. The same approach was used for developing anisotropic particles with magnetic or electric responses. A volumetric isotropic medium was made up consecutively from unit cells with cubic symmetry of the particles, and in parallel by random or quasi-periodic location

  13. 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.

  14. Optically induced 'negative forces'

    NASA Astrophysics Data System (ADS)

    Dogariu, Aristide; Sukhov, Sergey; Sáenz, José

    2013-01-01

    Attracting objects with optical beams may seem like science fiction, but various schemes already do this, albeit with some caveats and limitations. The most recent progress in this emerging field is reviewed, with particular emphasis on manipulation of small objects by optically induced 'negative forces'.

  15. Inventing Negative Numbers

    NSDL National Science Digital Library

    2008-10-10

    In this quick time video segment from Cyberchase, viewers learn about extending a vertical number line below zero as they watch the CyberSquad rescue the Cyberspace Council, which is being held captive by Hacker in a tall building. This video is also featured in the lesson plan: "Introducing Negative Numbers" (cataloged separately). Teaching Tips and a transcript are included.

  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. Determining the cosmic ray ionization rate in dynamically evolving clouds

    E-print Network

    C. J. Lintott; J. M. C. Rawlings

    2005-11-02

    The ionization fraction is an important factor in determining the chemical and physical evolution of star forming regions. In the dense, dark starless cores of such objects, the ionization rate is dominated by cosmic rays; it is therefore possible to use simple analytic estimators, based on the relative abundances of different molecular tracers, to determine the cosmic ray ionization rate. This paper uses a simple model to investigate the accuracy of two well-known estimators in dynamically evolving molecular clouds. It is found that, although the analytical formulae based on the abundances of H3+,H2,CO,O,H2O and HCO+ give a reasonably accurate measure of the cosmic ray ionization rate in static, quiescent clouds, significant discrepancies occur in rapidly evolving (collapsing) clouds. As recent evidence suggests that molecular clouds may consist of complex, dynamically evolving sub-structure, we conclude that simple abundance ratios do not provide reliable estimates of the cosmic ray ionization rate in dynamically active regions.

  18. 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

  19. Electron-impact ionization of Se2+

    NASA Astrophysics Data System (ADS)

    Alna'washi, G. A.; Aryal, N. B.; Baral, K. K.; Thomas, C. M.; Phaneuf, R. A.

    2014-07-01

    Absolute cross sections for electron-impact single and multiple ionization of Se2+ ions were measured using the dynamic-crossed-beams technique over the energy range from the ionization threshold to 500 eV and compared to direct ionization cross sections predicted by the Lotz semi-empirical formula. The single-ionization cross section appears to be dominated by excitation-autoionization of the 4s and 3d inner subshells. The double-ionization measurements are reasonably well accounted for by the semi-empirical fitting formula of Shevelko et al that includes both direct double ionization of the outer 4p subshell and single ionization of the 3p and 3d subshells followed by autoionization. In addition to direct triple ionization, 3p and 3s ionization followed by double autoionization and excitation of the 3p and 3s subshells followed by triple autoionization likely contribute to the triple ionization cross section.

  20. Effect of ionization mode in the analysis of proteolytic protein digests

    NASA Astrophysics Data System (ADS)

    Bigwarfe, Paul M.; Wood, Troy D.

    2004-05-01

    The bottom-up sequencing approach relies on an accurate mass fingerprint of the peptide fragments produced from enzymatic digestion. However, this technique is complicated by "dirty" mass spectra due to matrix interferences and, especially with regard to electrospray ionization data, the presence of multiply-charged species, both of which produce false and incorrect hits in database searches. Here, it is shown that the quality of mass spectra of peptide digests can be improved significantly by changing the polarity of the mass spectrometer's ionization source. Using the negative ion mode in both matrix-assisted laser desorption ionization and electrospray ionization of peptide digests results in the detection of a number of peaks in the mass spectra that are not observed in positive ion mode. In addition, there is considerable reduction in interference from contaminant species in the negative ion mode versus the positive ion mode. By combining the positive ion and negative ion mode data, greater sequence coverage and improved database search scores were obtained. When digestion is incomplete, a dramatic enrichment in the observed abundances for digest product peptides versus the intact proteins could be obtained by changing the pH and the ionization mode. The present results highlight the importance of using positive ion mode and negative ion mode combined to improve overall amino acid sequence coverage and improve confidence in protein identification.