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Sample records for atmospheric-pressure chemical ionization

  1. Establishing Atmospheric Pressure Chemical Ionization Efficiency Scale.

    PubMed

    Rebane, Riin; Kruve, Anneli; Liigand, Piia; Liigand, Jaanus; Herodes, Koit; Leito, Ivo

    2016-04-01

    Recent evidence has shown that the atmospheric pressure chemical ionization (APCI) mechanism can be more complex than generally assumed. In order to better understand the processes in the APCI source, for the first time, an ionization efficiency scale for an APCI source has been created. The scale spans over 5 logIE (were IE is ionization efficiency) units and includes 40 compounds with a wide range of chemical and physical properties. The results of the experiments show that for most of the compounds the ionization efficiency order in the APCI source is surprisingly similar to that in the ESI source. Most of the compounds that are best ionized in the APCI source are not small volatile molecules. Large tetraalkylammonium cations are a prominent example. At the same time, low-polarity hydrocarbons pyrene and anthracene are ionized in the APCI source but not in the ESI source. These results strongly imply that in APCI several ionization mechanisms operate in parallel and a mechanism not relying on evaporation of neutral molecules from droplets has significantly higher influence than commonly assumed. PMID:26943482

  2. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization

    NASA Astrophysics Data System (ADS)

    Vaikkinen, Anu; Kauppila, Tiina J.; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M+. decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques.

  3. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization

    NASA Astrophysics Data System (ADS)

    Vaikkinen, Anu; Kauppila, Tiina J.; Kostiainen, Risto

    2016-04-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M+. decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques.

  4. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization.

    PubMed

    Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M(+.) decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. Graphical Abstract ᅟ. PMID:27126470

  5. Comparison of electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization for a lipidomic analysis of Leishmania donovani.

    PubMed

    Imbert, Laurent; Gaudin, Mathieu; Libong, Danielle; Touboul, David; Abreu, Sonia; Loiseau, Philippe M; Laprévote, Olivier; Chaminade, Pierre

    2012-06-15

    A comparison of electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) for the analysis of a wide range of lipids has been performed on standard mixtures and extracts of Leishmania donovani promastigotes resistant to Amphotericin B (AmB). Calibration model, precision, limits of detection and quantification (LOD and LOQ) were assessed for each source. APPI provided the highest signal, signal-to-noise (S/N), and sensitivity for non-polar and low-polarity lipids, while ESI and APCI gave better results for the most polar ones. The linear model was valid for all lipids, except for one class with APPI, six classes with ESI, and eleven classes with APCI. LODs ranged from 0.2 to 20 μg mL(-1) for ESI, from 0.1 to 10 μg mL(-1) for APCI, and from 0.02 to 9.5 μg mL(-1) for APPI. LOQs ranged from 0.2 to 61 μg mL(-1) for ESI, from 0.4 to 31 μg mL(-1) for APCI, and from 0.1 to 29 μg mL(-1) for APPI. Each source provided similar lipid composition and variations in a comparison of three different L. donovani samples: miltefosine-treated, miltefosine-resistant and treated miltefosine-resistant parasites. A treated miltefosine-resistant sample was finally analyzed with each ion source in order to verify that the same lipid molecular species are detected. PMID:22560453

  6. Characteristics of low-temperature plasma ionization for ambient mass spectrometry compared to electrospray ionization and atmospheric pressure chemical ionization.

    PubMed

    Albert, Anastasia; Engelhard, Carsten

    2012-12-18

    Ambient desorption/ionization mass spectrometry (ADI-MS) is an attractive method for direct analysis with applications in homeland security, forensics, and human health. For example, low-temperature plasma probe (LTP) ionization was successfully used to detect, e.g., explosives, drugs, and pesticides directly on the target. Despite the fact that the field is gaining significant attention, few attempts have been made to classify ambient ionization techniques based on their ionization characteristics and performance compared to conventional ionization sources used in mass spectrometry. In the present study, relative ionization efficiencies (RIEs) for a large group of compound families were determined with LTP-Orbitrap-MS and compared to those obtained with electrospray ionization mass spectrometry (ESI-MS) and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). RIEs were normalized against one reference compound used across all methods to ensure comparability of the results. Typically, LTP analyte ionization through protonation/deprotonation (e.g., 4-acetamidophenol) was observed; in some cases (e.g., acenaphthene) radicals were formed. Amines, amides, and aldehydes were ionized successfully with LTP. A benefit of LTP over conventional methods is the possibility to successfully ionize PAHs and imides. Here, the studied model compounds could be detected by neither APCI nor ESI. LTP is a relatively soft ionization method because little fragmentation of model compounds was observed. It is considered to be an attractive method for the ionization of low molecular weight compounds over a relatively wide polarity range. PMID:23134531

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

    PubMed

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

    2011-07-30

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

  8. Rotation planar chromatography coupled on-line with atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Van Berkel, Gary J; Llave, Jonathan J; De Apadoca, Marilyn F; Ford, Michael J

    2004-01-15

    The coupling of a rotation planar preparative thin-layer chromatography system on-line with mass spectrometry is demonstrated using a simple plumbing scheme and a self-aspirating heated nebulizer probe of a corona discharge atmospheric pressure chemical ionization source. The self-aspiration of the heated nebulizer delivers approximately 20 microL/min of the 3.0 mL/min eluate stream to the mass spectrometer, eliminating the need for an external pump in the system. The viability of the coupling is demonstrated with a three-dye mixture composed of fat red 7B, solvent green 3, and solvent blue 35 separated and eluted from a silica gel-coated rotor using toluene. The real-time characterization of the dyes eluting from the rotor is illustrated in positive ion full-scan mode. Other self-aspirating ion source systems including atmospheric pressure photoionization, electrospray ionization, and inductively coupled plasma ionization, for example, might be configured and used in a similar manner coupled to the chromatograph to expand the types of analytes that could be ionized, detected, and characterized effectively. PMID:14719901

  9. 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.

  10. Medium Vacuum Electron Emitter as Soft Atmospheric Pressure Chemical Ionization Source for Organic Molecules.

    PubMed

    Liedtke, Sascha; Ahlmann, Norman; Marggraf, Ulrich; Schütz, Alexander; Vautz, Wolfgang; Franzke, Joachim

    2016-05-01

    An electron emitter as a soft atmospheric pressure chemical ionization source is presented, which operates at inner pressures of the device in the medium vacuum range (>10(-3) hPa). Conventional nonradioactive electron emitters require high vacuum (<10(-6) hPa) to prevent electrical sparkovers. The emitter presented here contains structural modifications of an existing setup, which inhibits electrical breakdowns up to 10(-2) hPa at 8 kV acceleration voltage. The increased inner pressure reduces the ionization efficiency until 10(-3) hPa-achievable without a turbomolecular pump-by 2% compared to high-vacuum conditions. This can be compensated with an increase of the electron source output. The functionality of this ion source is demonstrated with mass spectrometric and ion mobility measurements of acetone, eucalyptol, and diisopropyl methanephosphonate. Additional mass spectrometric measurements of 20 different organic compounds demonstrate the soft characteristics of this ionization source. PMID:27046293

  11. 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.

  12. 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

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

    PubMed Central

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

    2010-01-01

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

  14. 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.

  15. Gas phase studies on terpenes by ion mobility spectrometry using different atmospheric pressure chemical ionization techniques

    NASA Astrophysics Data System (ADS)

    Borsdorf, H.; Stone, J. A.; Eiceman, G. A.

    2005-11-01

    The ionization pathways and drift behavior were determined for sets of constitutional isomeric and stereoisomeric non-polar hydrocarbons (unsaturated monocyclic terpenes, unsaturated and saturated bicyclic terpenes) using ion mobility spectrometry (IMS) with different techniques of atmospheric pressure chemical ionization (APCI) to assess how structural and stereochemical differences influence ion formation. Depending on the structural features, different ions were observed for constitutional isomers using ion mobility spectrometry with photoionization (PI) and corona discharge (CD) ionization. Photoionization provides ion mobility spectra containing one major peak for saturated compounds while at two peaks were observed for unsaturated compounds, which can be assigned to product ions related to monomer and dimer ions. However, differences in relative abundance of product ions were found depending on the position of the double bond. Although IMS using corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra are complex and differ from those obtained using photoionization. Additional cluster ions and fragment ions were detected. Only small differences in ion mobility spectra were observed for the diastereomers while the enantiomers provide identical spectra. The structure of the product ions formed was checked by investigations using the coupling of ion mobility spectrometry with mass spectrometry (IMS-MS).

  16. Determination of nicarbazin in eggs by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Blanchflower, W J; Hughes, P J; Kennedy, D G

    1997-01-01

    A method was developed to determine in eggs 2 components [4,6-dimethyl-2-hydroxypyrimidine and 1,3-bis(4-nitrophenyl)urea] of the anticoccidial drug nicarbazin, used to treat poultry. Samples were extracted with acetonitrile, and the extracts were washed with hexane and evaporated to dryness before analysis by liquid chromatography/mass spectrometry with atmospheric pressure chemical ionization. By switching from positive to negative ion monitoring and using gradient elution, both components were measured within one run. The limit of quantitation of the assay was 10 ng/g for each component. The results of a preliminary feeding trial in which chickens were fed contamination levels of the drug are also reported. PMID:9419856

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2006-05-01

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

  19. Characterization of triacetone triperoxide by ion mobility spectrometry and mass spectrometry following atmospheric pressure chemical ionization

    SciTech Connect

    Ewing, Robert G.; Waltman, Melanie J.; Atkinson, David A.

    2011-04-28

    The atmospheric pressure chemical ionization of triacetone triperoxide (TATP) with subsequent separation and detection by ion mobility spectrometry has been studied. Positive ionization with hydronium reactant ions produced only fragments of the TATP molecule, with m/z 91 ion being the most predominant species. Ionization with ammonium reactant ions produced a molecular adduct at m/z 240. The reduced mobility value of this ion was constant at 1.36 cm{sup 2}V{sup -1}s{sup -1} across the temperature range from 60 to 140 C. The stability of this ion was temperature dependent and did not exist at temperatures above 140 C, where only fragment ions were observed. The introduction of ammonia vapors with TATP resulted in the formation of m/z 58 ion. As the concentration of ammonia increased, this smaller ion appeared to dominate the spectra and the TATP-ammonium adduct decreased in intensity. The ion at m/z 58 has been noted by several research groups upon using ammonia reagents in chemical ionization, but the identity was unknown. Evidence presented here supports the formation of protonated 2-propanimine. A proposed mechanism involves the addition of ammonia to the TATP-ammonium adduct followed by an elimination reaction. A similar mechanism involving the chemical ionization of acetone with excess ammonia also showed the formation of m/z 58 ion. TATP vapors from a solid sample were detected with a hand-held ion mobility spectrometer operated at room temperature. The TATP-ammonium molecular adduct was observed in the presence of ammonia and TATP vapors with this spectrometer.

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

    NASA Astrophysics Data System (ADS)

    Harris, Glenn A.

    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.

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

    SciTech Connect

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

    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.

  2. 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.

  3. Gas Chromatography/Atmospheric Pressure Chemical Ionization Tandem Mass Spectrometry for Fingerprinting the Macondo Oil Spill.

    PubMed

    Lobodin, Vladislav V; Maksimova, Ekaterina V; Rodgers, Ryan P

    2016-07-01

    We report the first application of a new mass spectrometry technique (gas chromatography combined to atmospheric pressure chemical ionization tandem mass spectrometry, GC/APCI-MS/MS) for fingerprinting a crude oil and environmental samples from the largest accidental marine oil spill in history (the Macondo oil spill, the Gulf of Mexico, 2010). The fingerprinting of the oil spill is based on a trace analysis of petroleum biomarkers (steranes, diasteranes, and pentacyclic triterpanes) naturally occurring in crude oil. GC/APCI enables soft ionization of petroleum compounds that form abundant molecular ions without (or little) fragmentation. The ability to operate the instrument simultaneously in several tandem mass spectrometry (MS/MS) modes (e.g., full scan, product ion scan, reaction monitoring) significantly improves structural information content and sensitivity of analysis. For fingerprinting the oil spill, we constructed diagrams and conducted correlation studies that measure the similarity between environmental samples and enable us to differentiate the Macondo oil spill from other sources. PMID:27281271

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

    PubMed

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

    2010-10-01

    A novel strategy to trace the origins of commercial pharmaceutical products has been developed based on the direct chemical profiling of the pharmaceutical products by surface desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS). Besides the unambiguous identification of active drug components, various compounds present in the matrixes are simultaneously detected without sample pretreatment, providing valuable information for drug quality control and origin differentiation. Four sources of commercial amoxicillin products made by different manufacturers have been successfully differentiated. This strategy has been extended to secerning six sources of Liuwei Dihuang Teapills, which are herbal medicine preparations with extremely complex matrixes. The photolysis status of chemical drug products and the inferior natural herd medicine products prepared with different processes (e.g., extra heating) were also screened using the method reported here. The limit of detection achieved in the MS/MS experiments was estimated to be 1 ng/g for amoxicillin inside the capsule product. Our experimental data demonstrate that DAPCI-MS is a useful tool for rapid pharmaceutical analysis, showing promising perspectives for tracking the entire pharmaceutical supply chain to prevent counterfeit intrusions. PMID:20809628

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

    PubMed

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

    2014-08-19

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

  6. Differentiation of (Mixed) Halogenated Dibenzo-p-Dioxins by Negative Ion Atmospheric Pressure Chemical Ionization.

    PubMed

    Fernando, Sujan; Green, M Kirk; Organtini, Kari; Dorman, Frank; Jones, Rhys; Reiner, Eric J; Jobst, Karl J

    2016-05-17

    Brominated and mixed halogenated dibenzo-p-dioxins (PBDDs and PXDDs) may well be as toxic as 2,3,7,8-tetrachloro-dibenzo-p-dioxin (2378-TCDD), a compound reputed as one of the most toxic chemicals known to exist. However, studies on the occurrence of PXDDs have been hampered by a lack of authentic standards as well as separation techniques capable of resolving the enormous number of potential isomers. Electron ionization (EI) mass spectrometry based methods are of limited value due to the lack of isomer specific fragmentation. Negative ion atmospheric pressure chemical ionization (APCI(-)) of 2378-TCDD was described in this journal over 30 years ago. Under these conditions, the reaction between O2(-•) and 2378-TCDD results in structure diagnostic cleavages of the C-O bonds, which can distinguish TCDD isomers on the basis of Cl distribution between the two aromatic rings. In the present study, the analogous ether cleavages of PBDDs and PXDDs were studied using a gas chromatograph-quadrupole time-of-flight (GC-QTOF) mass spectrometer coupled using APCI. The results indicate comparable detection limits for the radical cations [M(•+)] and negative pseudomolecular ions [M-Cl+O](-): approximately 5 fg and 10 fg, respectively, for 2378-TCDD and 5-10 fg and 10-30 fg, respectively, for the 2,3,7,8-substituted PXDDs. Detection limits obtained by monitoring the ether cleavage products were somewhat higher (between 100 and 600 fg) but still acceptable for trace analysis of PXDDs. Such reactions may resolve coeluting isomers, which is crucial for the identification of PXDDs. The technique is demonstrated by differentiating PXDD isomer classes in a sample obtained from a major industrial fire that would not be feasible using EI or positive ion APCI(+). PMID:27074061

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

    PubMed

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

    2015-04-01

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

  8. 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.

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

    PubMed

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

    2006-07-01

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

  10. Unexpected observation of ion suppression in a liquid chromatography/atmospheric pressure chemical ionization mass spectrometric bioanalytical method.

    PubMed

    Sangster, Tim; Spence, Mike; Sinclair, Peta; Payne, Richard; Smith, Christopher

    2004-01-01

    Ion suppression is a well-known phenomenon in electrospray ionization (ESI) mass spectrometry. These suppression effects have been shown to adversely affect the accuracy and precision of quantitative bioanalytical methods using ion spray. Such suppression effects have not been as well defined in atmospheric pressure chemical ionization (APCI) and there is some debate whether these effects actually occur in the ionization process using APCI. Here an example is described where clear ion suppression was observed during studies on a model compound and three metabolites using APCI liquid chromatography/tandem mass spectrometry (LC/MS/MS). PMID:15174192

  11. Secondary ionization of chemical warfare agent simulants: atmospheric pressure ion mobility time-of-flight mass spectrometry.

    PubMed

    Steiner, Wes E; Clowers, Brian H; Haigh, Paul E; Hill, Herbert H

    2003-11-15

    For the first time, the use of a traditional ionization source for ion mobility spectrometry (radioactive nickel ((63)Ni) beta emission ionization) and three alternative ionization sources (electrospray ionization (ESI), secondary electrospray ionization (SESI), and electrical discharge (corona) ionization (CI)) were employed with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer (IM(tof)MS) to detect chemical warfare agent (CWA) simulants from both aqueous- and gas-phase samples. For liquid-phase samples, ESI was used as the sample introduction and ionization method. For the secondary ionization (SESI, CI, and traditional (63)Ni ionization) of vapor-phase samples, two modes of sample volatilization (heated capillary and thermal desorption chamber) were investigated. Simulant reference materials, which closely mimic the characteristic chemical structures of CWA as defined and described by Schedule 1, 2, or 3 of the Chemical Warfare Convention treaty verification, were used in this study. A mixture of four G/V-type nerve simulants (dimethyl methylphosphonate, pinacolyl methylphosphonate, diethyl phosphoramidate, and 2-(butylamino)ethanethiol) and one S-type vesicant simulant (2-chloroethyl ethyl sulfide) were found in each case (sample ionization and introduction methods) to be clearly resolved using the IM(tof)MS method. In many cases, reduced mobility constants (K(o)) were determined for the first time. Ion mobility drift times, flight times, relative signal intensities, and fragmentation product signatures for each of the CWA simulants are reported for each of the methods investigated. PMID:14615983

  12. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    We propose detecting a fragment ion (Ph2As+) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH+) of DA, DC, DPAH, and BDPAO could produce Ph2As+ through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As+ signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH+ signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As+.

  13. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

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

    2016-07-01

    We propose detecting a fragment ion (Ph2As(+)) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH(+)) of DA, DC, DPAH, and BDPAO could produce Ph2As(+) through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As(+) signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH(+) signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As(+). Graphical Abstract ᅟ. PMID:27098411

  14. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    We propose detecting a fragment ion (Ph2As+) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH+) of DA, DC, DPAH, and BDPAO could produce Ph2As+ through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As+ signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH+ signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As+.

  15. Hydrogen/deuterium exchange on aromatic rings during atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Davies, Noel W; Smith, Jason A; Molesworth, Peter P; Ross, John J

    2010-04-15

    It has been demonstrated that substituted indoles fully labelled with deuterium on the aromatic ring can undergo substantial exchange back to partial and even fully protonated forms during atmospheric pressure chemical ionisation (APCI) liquid chromatography/mass spectrometry (LC/MS). The degree of this exchange was strongly dependent on the absolute quantity of analyte, the APCI desolvation temperature, the nature of the mobile phase, the mobile phase flow rate and the instrument used. Hydrogen/deuterium (H/D) exchange on several other aromatic ring systems during APCI LC/MS was either undetectable (nitrobenzene, aniline) or extremely small (acetanilide) compared to the effect observed for substituted indoles. This observation has major implications for quantitative assays using deuterium-labelled internal standards and for the detection of deuterium-labelled products from isotopically labelled feeding experiments where there is a risk of back exchange to the protonated form during the analysis. PMID:20213724

  16. Benzylammonium Thermometer Ions: Internal Energies of Ions Formed by Low Temperature Plasma and Atmospheric Pressure Chemical Ionization.

    PubMed

    Stephens, Edward R; Dumlao, Morphy; Xiao, Dan; Zhang, Daming; Donald, William A

    2015-12-01

    The extent of internal energy deposition upon ion formation by low temperature plasma and atmospheric pressure chemical ionization was investigated using novel benzylammonium thermometer ions. C-N heterolytic bond dissociation enthalpies of nine 4-substituted benzylammoniums were calculated using CAM-B3LYP/6-311++G(d,p), which was significantly more accurate than B3LYP/6-311++G(d,p), MP2/6-311++G(d,p), and CBS-QB3 for calculating the enthalpies of 20 heterolytic dissociation reactions that were used to benchmark theory. All 4-substituted benzylammonium thermometer ions fragmented by a single pathway with comparable dissociation entropies, except 4-nitrobenzylammonium. Overall, the extent of energy deposition into ions formed by low temperature plasma was significantly lower than those formed by atmospheric pressure chemical ionization under these conditions. Because benzylamines are volatile, this new suite of thermometer ions should be useful for investigating the extent of internal energy deposition during ion formation for a wide range of ionization methods, including plasma, spray and laser desorption-based techniques. Graphical Abstract ᅟ. PMID:26438128

  17. Benzylammonium Thermometer Ions: Internal Energies of Ions Formed by Low Temperature Plasma and Atmospheric Pressure Chemical Ionization

    NASA Astrophysics Data System (ADS)

    Stephens, Edward R.; Dumlao, Morphy; Xiao, Dan; Zhang, Daming; Donald, William A.

    2015-12-01

    The extent of internal energy deposition upon ion formation by low temperature plasma and atmospheric pressure chemical ionization was investigated using novel benzylammonium thermometer ions. C-N heterolytic bond dissociation enthalpies of nine 4-substituted benzylammoniums were calculated using CAM-B3LYP/6-311++G(d,p), which was significantly more accurate than B3LYP/6-311++G(d,p), MP2/6-311++G(d,p), and CBS-QB3 for calculating the enthalpies of 20 heterolytic dissociation reactions that were used to benchmark theory. All 4-substituted benzylammonium thermometer ions fragmented by a single pathway with comparable dissociation entropies, except 4-nitrobenzylammonium. Overall, the extent of energy deposition into ions formed by low temperature plasma was significantly lower than those formed by atmospheric pressure chemical ionization under these conditions. Because benzylamines are volatile, this new suite of thermometer ions should be useful for investigating the extent of internal energy deposition during ion formation for a wide range of ionization methods, including plasma, spray and laser desorption-based techniques.

  18. Atmospheric Pressure Chemical Ionization Sources Used in The Detection of Explosives by Ion Mobility Spectrometry

    SciTech Connect

    Waltman, Melanie J.

    2010-05-01

    Explosives detection is a necessary and wide spread field of research. From large shipping containers to airline luggage, numerous items are tested for explosives every day. In the area of trace explosives detection, ion mobility spectrometry (IMS) is the technique employed most often because it is a quick, simple, and accurate way to test many items in a short amount of time. Detection by IMS is based on the difference in drift times of product ions through the drift region of an IMS instrument. The product ions are created when the explosive compounds, introduced to the instrument, are chemically ionized through interactions with the reactant ions. The identity of the reactant ions determines the outcomes of the ionization process. This research investigated the reactant ions created by various ionization sources and looked into ways to manipulate the chemistry occurring in the sources.

  19. Potential of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry for screening and quantification of hexabromocyclododecane.

    PubMed

    Sales, Carlos; Portolés, Tania; Sancho, Juan Vicente; Abad, Esteban; Ábalos, Manuela; Sauló, Jordi; Fiedler, Heidelore; Gómara, Belén; Beltrán, Joaquim

    2016-01-01

    A fast method for the screening and quantification of hexabromocyclododecane (sum of all isomers) by gas chromatography using a triple quadrupole mass spectrometer with atmospheric pressure chemical ionization (GC-APCI-QqQ) is proposed. This novel procedure makes use of the soft atmospheric pressure chemical ionization source, which results in less fragmentation of the analyte than by conventional electron impact (EI) and chemical ionization (CI) sources, favoring the formation of the [M - Br](+) ion and, thus, enhancing sensitivity and selectivity. Detection was based on the consecutive loses of HBr from the [M - Br](+) ion to form the specific [M - H5Br6](+) and [M - H4Br5](+) ions, which were selected as quantitation (Q) and qualification (q) transitions, respectively. Parameters affecting ionization and MS/MS detection were studied. Method performance was also evaluated; calibration curves were found linear from 1 pg/μL to 100 pg/μL for the total HBCD concentration; instrumental detection limit was estimated to be 0.10 pg/μL; repeatability and reproducibility, expressed as relative standard deviation, were better than 7% in both cases. The application to different real samples [polyurethane foam disks (PUFs), food, and marine samples] pointed out a rapid way to identify and allow quantification of this compound together with a number of polybrominated diphenyl ethers (BDE congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two other novel brominated flame retardants [i.e., decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)] because of their presence in the same fraction when performing the usual sample treatment. PMID:26554601

  20. A corona discharge atmospheric pressure chemical ionization source with selective NO(+) formation and its application for monoaromatic VOC detection.

    PubMed

    Sabo, Martin; Matejčík, Štefan

    2013-11-21

    We have developed a new type of corona discharge (CD) for atmospheric pressure chemical ionization (APCI) for application in ion mobility spectrometry (IMS) as well as in mass spectrometry (MS). While the other CD-APCI sources are able to generate H3O(+)·(H2O)n as the major reactant ions in N2 or in zero air, the present CD-APCI source has the ability to generate up to 84% NO(+)·(H2O)n reactant ions in zero air. The change of the working gas from zero air to N2 allows us to change the major reactant ions from NO(+)·(H2O)n to H3O(+)·(H2O)n. In this paper we present the description of the new CD-APCI and discuss the processes associated with the NO(+) formation. The selective formation of NO(+)·(H2O)n reactant ions offers chemical ionization based on these ions which can be of great advantage for some classes of chemicals. We demonstrate here a significant increase in the sensitivity of the IMS-MS instrument for monoaromatic volatile organic compound (VOC) detection upon NO(+)·(H2O)n chemical ionization. PMID:24081306

  1. Formation of Metal-Adducted Analyte Ions by Flame-Induced Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

    Cheng, Sy-Chyi; Wang, Chin-Hsiung; Shiea, Jentaie

    2016-05-17

    A flame-induced atmospheric pressure chemical ionization (FAPCI) source, consisting of a miniflame, nebulizer, and heated tube, was developed to ionize analytes. The ionization was performed by reacting analytes with a charged species generated in a flame. A stainless steel needle deposited with saturated alkali chloride solution was introduced into the mini oxyacetylene flame to generate alkali ions, which were reacted with analytes (M) generated in a heated nebulizer. The alkali-adducted 18-crown-6 ether ions, including (M + Li)(+), (M + Na)(+), (M + K)(+), (M + Rb)(+), and (M + Cs)(+), were successfully detected on the FAPCI mass spectra when the corresponding alkali chloride solutions were separately introduced to the flame. When an alkali chloride mixture was introduced, all alkali-adducted analyte ions were simultaneously detected. Their intensity order was as follows: (M + Cs)(+) > (M + Rb)(+) > (M + K)(+) > (M + Na)(+) > (M + Li)(+), and this trend agreed with the lattice energies of alkali chlorides. Besides alkali ions, other transition metal ions such as Ni(+), Cu(+), and Ag(+) were generated in a flame for analyte ionization. Other than metal ions, the reactive species generated in the fossil fuel flame could also be used to ionize analytes, which formed protonated analyte ions (M + H)(+) in positive ion mode and deprotonated analyte ions (M - H)(-) in negative ion mode. PMID:27093572

  2. 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

  3. On-line characterization of organic aerosols formed from biogenic precursors using atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Kückelmann, U; Warscheid, B; Hoffmann, T

    2000-04-15

    A method to investigate the chemical composition of organic aerosols formed from biogenic hydrocarbon oxidation using atmospheric pressure chemical ionization mass spectrometry (APCI/MS) is described. The method involves the direct introduction of aerosol particles into the ion source of the mass spectrometer. Using this technique, reaction monitoring experiments of alpha-pinene ozonolysis show the formation of hetero- and homomolecular cluster anions (dimers) of the primary oxidation products (multifunctional carboxylic acids). Since the formation of dimers plays a profound role in new particle formation processes by homogeneous nucleation in the atmosphere and, at the same time, is an intrinsic feature of APCI, it is essential to differentiate between both processes when on-line APCI/MS is applied. In this paper, we compare the results from the investigations of organic aerosols and artificially generated dimer cluster ions of the same compounds using identical ionization conditions. The clusters and their formation processes are characterized by varying the analyte concentration, investigating the thermal stability of dimers, and studying collisional activation properties of both ion species. The investigations show a significant difference in ion stability: dimer anions measured on-line have an estimated stability that is 20 kJ mol(-1) higher than that of the corresponding artificially generated cluster ions. Hence, the technique provides the possibility to accurately characterize dimers as ionized reaction products from biogenic hydrocarbon oxidation and allows an insight into the process of new-particle formation by homogeneous nucleation. PMID:10784160

  4. Gas Chromatography Coupled to Atmospheric Pressure Chemical Ionization FT-ICR Mass Spectrometry for Improvement of Data Reliability.

    PubMed

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

    2015-12-15

    Atmospheric pressure chemical ionization (APCI) offers the advantage of molecular ion information with low fragmentation. Hyphenating APCI to gas chromatography (GC) and ultrahigh resolution mass spectrometry (FT-ICR MS) enables an improved characterization of complex mixtures. Data amounts acquired by this system are very huge, and existing peak picking algorithms are usually extremely time-consuming, if both gas chromatographic and ultrahigh resolution mass spectrometric data are concerned. Therefore, automatic routines are developed that are capable of handling these data sets and further allow the identification and removal of known ionization artifacts (e.g., water- and oxygen-adducts, demethylation, dehydrogenation, and decarboxylation). Furthermore, the data quality is enhanced by the prediction of an estimated retention index, which is calculated simply from exact mass data combined with a double bond equivalent correction. This retention index is used to identify mismatched elemental compositions. The approach was successfully tested for analysis of semivolatile components in heavy fuel oil and diesel fuel as well as primary combustion particles emitted by a ship diesel research engine. As a result, 10-28% of the detected compounds, mainly low abundant species, classically assigned by using only the mass spectrometric information, were identified as not valid and removed. Although GC separation is limited by the slow acquisition rate of the FT-ICR MS (<1 Hz), a database driven retention time comparison, as commonly used for low resolution GC/MS, can be applied for revealing isomeric information. PMID:26560682

  5. 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.

  6. 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.

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

    SciTech Connect

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

    2005-01-01

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

  8. Post-Blast Analysis of Hexamethylene Triperoxide Diamine using Liquid Chromatography-Atmospheric Pressure Chemical Ionization-Mass Spectrometry.

    PubMed

    Marsh, Christine M; Mothershead, Robert F; Miller, Mark L

    2015-09-01

    A qualitative method using liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC/APCI-MS) has been developed and validated for the identification of trace hexamethylene triperoxide diamine (HMTD) using three structurally-specific ions. Residues are extracted with deionized water (DI) and identified using a gradient mobile phase program and positive ion full scan mode on a Thermo Finnigan LCQ Ion Trap Mass Spectrometer. This method was validated according to several performance characteristics for the qualitative identification of an analyte using the characteristic ions, demonstrating the method's reliability for use on forensic applications. The method's limit of detection (LOD) can identify HMTD in an extract from a cotton matrix to which 20 μg of HMTD has been applied (equivalent to 10 ppm in extract). Previous scientific publications using LC/MS have not demonstrated post-blast HMTD residue analyses and suffer from a lack of chromatographic retention, sufficient number of mass spectral ions with validation, or require more complex/expensive instrumental methods (accurate mass or MS/MS). Post-blast analyses were successfully conducted with two syringe detonations that verified the efficacy of the method on the analysis of debris and residues following detonation. PMID:26385711

  9. Liquid chromatography/atmospheric pressure chemical ionization-mass spectrometric analysis of benzoylurea insecticides in citrus fruits.

    PubMed

    Valenzuela, A I; Picó, Y; Font, G

    2000-01-01

    A liquid chromatography (LC) method for the quantitative determination of three benzoylurea insecticide residues (diflubenzuron, flufenoxuron and hexaflumuron) in citrus fruits is described. Residues were successfully separated on a C18 column by methanol/water gradient elution. Detection was by negative-ion, selected-ion monitoring atmospheric pressure chemical ionization-mass spectrometry (APCI-MS); the main ions were [M - H]-, and the secondary fragment ions were [M - H - HF]-. Useful confirmatory information can thus be obtained at low extraction voltages from losses of HF. Detection limits for standard solutions were 10 fg injected and good linearity and reproducibility were obtained. The optimum LC/APCI-MS conditions were applied to the analysis of benzoylureas in oranges. Samples were extracted using matrix solid phase dispersion (MSPD), in which orange samples were homogenized with Cs, placed onto a glass column and eluted with dichloromethane. Detection limits of 2 microg kg(-1) in the crop were obtained. Average recoveries from citrus fortified with approximately (25-1000 microg kg(-1)) ranged from 87 to 102%. The method was applied to field-treated orange samples and benzoylureas were sometimes detected at concentration levels lower than maximum residue limits. PMID:10775090

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

    PubMed

    Helale, Murad I H; Tanaka, Kazuhiko; Taoda, Hiroshi; Hu, Wenzhi; Hasebe, Kiyoshi; Haddad, Paul R

    2002-05-17

    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 (APCI-MS). A mobile phase consisting of 0.85 mM benzoic acid in 10% aqueous methanol (pH 3.89) was used to separate the above carboxylic acids in about 40 min. For LC-MS, the APCI interface was used in the negative ionization mode. Linear plots of peak area versus concentration were obtained over the range 1-30 mM (r2=0.9982) and 1-30 mM (r2=0.9958) for conductimetric and MS detection, respectively. The detection limits of the target carboxylic acids calculated at S/N=3 ranged from 0.078 to 2.3 microM for conductimetric and photometric detection and from 0.66 to 3.82 microM for ion-exclusion chromatography-APCI-MS. The reproducibility of retention times was 0.12-0.16% relative standard deviation for ion-exclusion chromatography and 1.21-2.5% for ion-exclusion chromatography-APCI-MS. The method was applied to the determination of carboxylic acids in red wine, white wine, apple vinegar, and Japanese rice wine. PMID:12108651

  11. Determination of organic acids in ground water by liquid chromatography/atmospheric pressure chemical ionization/mass spectrometry

    SciTech Connect

    Fang, J.; Barcelona, M.J.

    1999-05-01

    Current methods of determining organic acids in ground water are labor-intensive, time-consuming and require a large volume of sample (100 milliliter to 1.0 liter). This paper reports a new method developed to determine aliphatic, alicyclic, and aromatic acids in ground water using liquid chromatography/atmospheric pressure chemical ionization/mass spectrometry (LC/APCI/MS). This method was shown to be fast (less than 1 hour), effective, and reproducible, requiring only 1.0 mL of ground-water sample. Ground water was pH-adjusted, filtered through 0.45 {micro}m filters and directly injected into the LC. A binary solvent system consisting of 40 mM of aqueous ammonium acetate and methanol and a C18 column were used for chromatographical separation. The APCI was operated under negative ionization mode. Selected ion monitoring (SIM) was used for detection and quantitation of the analytes. This method was applied to the analysis of organic acids in ground-water samples collected from an aquifer contaminated with JP-4 fuel hydrocarbons at Wurtsmith Air Force Base in Oscoda, Michigan. Aromatic acids identified in the contaminated ground water include o-, m-toluic acids (2- and 3-methylbenzoic acids), 2,6-dimethylbenzoic acid, 2,3,5-and 2,4,6-trimethylbenzoic acids and two additional trimethylbenzoic acids with unknown location of methylation. The detection of aromatic acids in groundwater from the KC-135 site provided evidence for in situ microbial degradation of hydrocarbons occurring in the aquifer.

  12. Hand-held portable desorption atmospheric pressure chemical ionization ion source for in situ analysis of nitroaromatic explosives.

    PubMed

    Jjunju, Fred P M; Maher, Simon; Li, Anyin; Syed, Sarfaraz U; Smith, Barry; Heeren, Ron M A; Taylor, Stephen; Cooks, R Graham

    2015-10-01

    A novel, lightweight (0.6 kg), solvent- and gas-cylinder-free, hand-held ion source based on desorption atmospheric pressure chemical ionization has been developed and deployed for the analysis of nitroaromatic explosives on surfaces in open air, offering portability for in-field analysis. A small, inexpensive, rechargeable lithium polymer battery was used to power the custom-designed circuitry within the device, which generates up to ±5 kV dc voltage to ignite a corona discharge plasma in air for up to 12 h of continuous operation, and allowing positive- and negative-ion mass spectrometry. The generated plasma is pneumatically transported to the surface to be interrogated by ambient air at a rate of 1-3.5 L/min, compressed using a small on-board diaphragm pump. The plasma source allows liquid or solid samples to be examined almost instantaneously without any sample preparation in the open environment. The advantages of low carrier gas and low power consumption (<6 W), as well as zero solvent usage, have aided in developing the field-ready, hand-held device for trigger-based, "near-real-time" sampling/ionization. Individual nitroaromatic explosives (such as 2,4,6-trinitrotoluene) can be easily detected in amounts as low as 5.8 pg with a linear dynamic range of at least 10 (10-100 pg), a relative standard deviation of ca. 7%, and an R(2) value of 0.9986. Direct detection of several nitroaromatic compounds in a complex mixture without prior sample preparation is demonstrated, and their identities are confirmed by tandem mass spectrometry fragmentation patterns. PMID:26329926

  13. Analysis of gaseous toxic industrial compounds and chemical warfare agent simulants by atmospheric pressure ionization mass spectrometry.

    PubMed

    Cotte-Rodríguez, Ismael; Justes, Dina R; Nanita, Sergio C; Noll, Robert J; Mulligan, Christopher C; Sanders, Nathaniel L; Cooks, R Graham

    2006-04-01

    The suitability of atmospheric pressure chemical ionization mass spectrometry as sensing instrumentation for the real-time monitoring of low levels of toxic compounds is assessed, especially with respect to public safety applications. Gaseous samples of nine toxic industrial compounds, NH3, H2S, Cl2, CS2, SO2, C2H4O, HBr, C6H6 and AsH3, and two chemical warfare agent simulants, dimethyl methylphosphonate (DMMP) and methyl salicylate (MeS), were studied. API-MS proves highly suited to this application, with speedy analysis times (<30 seconds), high sensitivity, high selectivity towards analytes, good precision, dynamic range and accuracy. Tandem MS methods were implemented in selected cases for improved selectivity, sensitivity, and limits of detection. Limits of detection in the parts-per-billion and parts-per-trillion range were achieved for this set of analytes. In all cases detection limits were well below the compounds' permissible exposure limits (PELs), even in the presence of added complex mixtures of alkanes. Linear responses, up to several orders of magnitude, were obtained over the concentration ranges studied (sub-ppb to ppm), with relative standard deviations less than 3%, regardless of the presence of alkane interferents. Receiver operating characteristic (ROC) curves are presented to show the performance trade-off between sensitivity, probability of correct detection, and false positive rate. A dynamic sample preparation system for the production of gas phase analyte concentrations ranging from 100 pptr to 100 ppm and capable of admixing gaseous matrix compounds and control of relative humidity and temperature is also described. PMID:16568176

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  15. 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, 5α-cholestane, cholesta-3,5-diene, squalene, and β-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

  16. Atmospheric-pressure Penning ionization mass spectrometry.

    PubMed

    Hiraoka, Kenzo; Fujimaki, Susumu; Kambara, Shizuka; Furuya, Hiroko; Okazaki, Shigemitsu

    2004-01-01

    A preliminary study on the atmospheric-pressure Penning ionization (APP(e)I) of gaseous organic compounds with Ar* has been made. The metastable argon atoms (Ar*: 11.55 eV for (3)P(2) and 11.72 eV for (3)P(0)) were generated by the negative-mode corona discharge of atmospheric-pressure argon gas. By applying a high positive voltage (+500 to +1000 V) to the stainless steel capillary for the sample introduction (0.1 mm i.d., 0.3 mm o.d.), strong ion signals could be obtained. The ions formed were sampled through an orifice into the vacuum and mass-analyzed by an orthogonal time-of-flight mass spectrometer. The major ions formed by APP(e)I are found to be molecular-related ions for alkanes, aromatics, and oxygen-containing compounds. Because only the molecules with ionization energies less than the internal energy of Ar* are ionized, the present method will be a selective and highly sensitive interface for gas chromatography/mass spectrometry. PMID:15384154

  17. Online measurement of biogenic organic acids in the boreal forest using atmospheric pressure chemical ionization mass spectrometry (APCI-MS)

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

    Emission of biogenic volatile organic compounds (BVOCs) by vegetation in the boreal forest and their subsequent atmospheric oxidation leads to the formation of secondary organic aerosol (SOA) which has important impacts on climate and human health. Oxidation of BVOCs produces a variety of mostly unidentified species in oxygenated organic aerosol (OOA). Presently aerosol mass spectrometers (AMS) are able to determine quantitative information about the relative oxygen to carbon content of organic aerosols and thereby reveal the photochemical age and volatility of organic aerosol by distinguishing between low volatile oxygenated organic aerosol (LV-OOA), semivolatile oxygenated organic aerosol (SV-OOA) and hydrocarbon like organic aerosol (HOA)[1]. However, the AMS can usually not be used to measure and quantify single organic compounds such as individual biogenic organic marker compounds. Here we show the results of online measurements of gas and particle phase biogenic acids during HUMPPA-COPEC 2010 at Hyytiälä, Finland. This was achieved by coupling a self built miniature Versatile Aerosol Concentration Enrichment System (mVACES) as described by Geller et al. [2] with an Atmospheric Pressure Chemical Ionization Ion Trap Mass Spectrometer (APCI IT MS; Hoffmann et al., [3]). The benefits of the on-line APCI-MS are soft ionization with little fragmentation compared to AMS, high measurement frequency and less sampling artifacts than in the common procedure of taking filter samples, extraction and detection with LC-MS. Furthermore, the ion trap of the instrument allows MS/MS experiments to be performed by isolation of single m/z ratios of selected molecular species. By subsequent addition of energy, the trapped ions form characteristic fragments which enable structural insight on the molecular level. Comparison of APCI-MS data to AMS data, acquired with a C-ToF-AMS [4], revealed a good correlation coefficient for total organics and sulphate. Furthermore, data show

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

    PubMed

    Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

    2014-05-01

    A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs. PMID:24678766

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

    PubMed

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

    2013-03-01

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

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

    PubMed

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

    2015-07-01

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

  1. Direct quantitative analysis of organic compounds in the gas and particle phase using a modified atmospheric pressure chemical ionization source in combination with ion trap mass spectrometry.

    PubMed

    Warscheid, Bettina; Kückelmann, Ulrich; Hoffmann, Thorsten

    2003-03-15

    A slightly modified atmospheric pressure chemical ionization source is employed for direct quantitative analysis of volatile or semivolatile organic compounds in air. The method described here is based on the direct introduction of an analyte in the gas or particle phase, or both, into the ion source of a commercial ion trap mass spectrometer. For quantitation, a standard solution is directly transferred into the vaporizer unit of the ion source via a deactivated fused-silica capillary by using the sheath liquid syringe pump, which is part of the mass spectrometer. The standard addition procedure is conducted by varying the pump rate of a diluted solution of the standard compound in methanol/water. A N2 sheath gas flow is applied for optimal vaporization and mixing with the analyte gas stream. By performing detailed reagent ion monitoring experiments, it is shown that the relative signal intensity of [M + H]+ ions is dependent on the relative humidity of the analyte gas stream as well as the composition and concentration of CI reagent ions. The method is validated by a comparison of the standard addition results with a calibration test gas of known concentration. To demonstrate the potential of atmospheric pressure chemical ionization mass spectrometry as a quantitative analytical technique for on-line investigations, a tropospherically relevant reaction is carried out in a 493-L reaction chamber at atmospheric pressure and 296 K in synthetic air at 50% relative humidity. Finally, the applicability of the technique to rapidly differentiate between analytes in the gas and particle phase is demonstrated. PMID:12659203

  2. 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.

  3. Differentiation of Regioisomeric Aromatic Ketocarboxylic Acids by Positive Mode Atmospheric Pressure Chemical Ionization Collision-Activated Dissociation Tandem Mass Spectrometry in a Linear Quadrupole Ion Trap Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Amundson, Lucas M.; Owen, Benjamin C.; Gallardo, Vanessa A.; Habicht, Steven C.; Fu, Mingkun; Shea, Ryan C.; Mossman, Allen B.; Kenttämaa, Hilkka I.

    2011-04-01

    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.

  4. Gas Chromatography/Atmospheric Pressure Chemical Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Pyrolysis Oil from German Brown Coal.

    PubMed

    Zuber, Jan; Kroll, Marius M; Rathsack, Philipp; Otto, Matthias

    2016-01-01

    Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols. PMID:27066076

  5. Gas Chromatography/Atmospheric Pressure Chemical Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Pyrolysis Oil from German Brown Coal

    PubMed Central

    Zuber, Jan; Kroll, Marius M.; Rathsack, Philipp; Otto, Matthias

    2016-01-01

    Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols. PMID:27066076

  6. 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.

  7. 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

  8. Determination of lincomycin and tylosin residues in honey using solid-phase extraction and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Thompson, Thomas S; Noot, Donald K; Calvert, Jane; Pernal, Stephen F

    2003-12-12

    An analytical method for the determination of residues of the antibiotic drugs lincomycin and tylosin in honey was developed. The procedure employed a solid-phase extraction for the isolation of lincomycin and tylosin from diluted honey samples. The antibiotic residues were subsequently analyzed by reversed-phase HPLC with atmospheric pressure chemical ionization mass spectrometric detection. Average analyte recoveries for lincomycin and tylosin ranged from 84 to 107% in replicate sets of honey samples fortified with drug concentrations of 0.01, 0.5, and 10 microg/g. The method detection limits were determined to be 0.007 and 0.01 microg/g for lincomycin and tylosin, respectively. PMID:14661747

  9. Non-disturbing characterization of natural organic matter (NOM) contained in clay rock pore water by mass spectrometry using electrospray and atmospheric pressure chemical ionization modes.

    PubMed

    Huclier-Markai, Sandrine; Landesman, Catherine; Rogniaux, Hélène; Monteau, Fabrice; Vinsot, Agnes; Grambow, Bernd

    2010-01-01

    We have investigated the composition of the mobile natural organic matter (NOM) present in Callovo-Oxfodian pore water using electrospray ionization mass spectrometry (ESI-MS), atmospheric pressure chemical ionization mass spectrometry (APCI-MS) and emission-excitation matrix (EEM) spectroscopy. The generation of knowledge of the composition, structure and size of mobile NOM is necessary if one wants to understand the interactions of these compounds with heavy metals/radionuclides, in the context of environmental studies, and particularly how the mobility of these trace elements is affected by mobile NOM. The proposed methodology is very sensitive in unambiguously identifying the in situ composition of dissolved NOM in water even at very low NOM concentration, due to innovative non-disturbing water sampling and ionization (ESI/APCI-MS) techniques. It was possible to analyze a quite exhaustive inventory of the small organic compounds of clay pore water without proceeding to any chemical treatment at naturally occurring concentration levels. The structural features observed were mainly acidic compounds and fatty acids as well as aldehydes and amino acids. PMID:20013952

  10. Determination of oxygen and nitrogen derivatives of polycyclic aromatic hydrocarbons in fractions of asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

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

    2015-12-01

    Liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization was used for the determination of polycyclic aromatic hydrocarbon derivatives, the oxygenated polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons, formed in asphalt fractions. Two different methods have been developed for the determination of five oxygenated and seven nitrated polycyclic aromatic hydrocarbons that are characterized by having two or more condensed aromatic rings and present mutagenic and carcinogenic properties. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all compounds. The detection limits of the methods ranged from 0.1 to 57.3 μg/L for nitrated and from 0.1 to 6.6 μg/L for oxygenated derivatives. The limits of quantification were in the range of 4.6-191 μg/L for nitrated and 0.3-8.9 μg/L for oxygenated derivatives. The methods were validated against a diesel particulate extract standard reference material (National Institute of Standards and Technology SRM 1975), and the obtained concentrations (two nitrated derivatives) agreed with the certified values. The methods were applied in the analysis of asphalt samples after their fractionation into asphaltenes and maltenes, according to American Society for Testing and Material D4124, where the maltenic fraction was further separated into its basic, acidic, and neutral parts following the method of Green. Only two nitrated derivatives were found in the asphalt sample, quinoline and 2-nitrofluorene, with concentrations of 9.26 and 2146 mg/kg, respectively, whereas no oxygenated derivatives were detected. PMID:26446274

  11. Enhanced metabolite profiling using a redesigned atmospheric pressure chemical ionization source for gas chromatography coupled to high-resolution time-of-flight mass spectrometry.

    PubMed

    Wachsmuth, Christian J; Hahn, Thomas A; Oefner, Peter J; Dettmer, Katja

    2015-09-01

    An improved atmospheric pressure chemical ionization (APCI II) source for gas chromatography-high-resolution time-of-flight mass spectrometry (GC-HRTOFMS) was compared to its first-generation predecessor for the analysis of fatty acid methyl esters, methoxime-trimethylsilyl derivatives of metabolite standards, and cell culture supernatants. Reductions in gas turbulences and chemical background as well as optimized heating of the APCI II source resulted in narrower peaks and higher repeatability in particular for late-eluting compounds. Further, APCI II yielded a more than fourfold median decrease in lower limits of quantification to 0.002-3.91 μM along with an average 20 % increase in linear range to almost three orders of magnitude with R (2) values above 0.99 for all metabolite standards investigated. This renders the overall performance of GC-APCI-HRTOFMS comparable to that of comprehensive two-dimensional gas chromatography (GC × GC)-electron ionization (EI)-TOFMS. Finally, the number of peaks with signal-to-noise ratios greater than 20 that could be extracted from metabolite fingerprints of pancreatic cancer cell supernatants upon switching from the APCI I to the APCI II source was more than doubled. Concomitantly, the number of identified metabolites increased from 36 to 48. In conclusion, the improved APCI II source makes GC-APCI-HRTOFMS a great alternative to EI-based GC-MS techniques in metabolomics and other fields. PMID:26092404

  12. Evaluation of ELISA kits followed by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry for the determination of organic pollutants in industrial effluents

    SciTech Connect

    Castillo, M.; Oubina, A.; Barcelo, D.

    1998-07-15

    Contaminated industrial effluents often contain a variety of organic pollutants which are difficult to analyze by standard GC-MS methods since they often miss the more polar or nonvolatile of these organic compounds. The identification of highly polar analytes by chemical or rapid biological techniques is needed for characterization of the effluents. The present work evaluates the use of enzyme linked immunosorbent assays (ELISA) kits for determining pentachlorophenol, carcinogenic PAHs and BTEX (benzene, toluene, ethylbenzene, and o-, m-, and p-xylene) among the organic analytes present in various industrial effluents from Europe. The analytical protocol applied for the evaluation of the kits was based on the use of ELISA followed by solid-phase extraction (SPE) for the preconcentration of a variety of organic pollutants such as pentachlorophenol, phthalates, and nonylphenol and final determination with LC-MS characterization using an atmospheric pressure chemical ionization (APCI) interface in the positive and negative ionization modes. The developed protocol permitted the unequivocal identification of target analytes such as pentachlorophenol, nonylphenol, dibutylphthalate, dimethylphthalate, bis(2-ethylhexyl)phthalate 2-methylbenzenesulfonamide, and 2,2-dimethylbenzene-sulfonamide present in industrial effluents. The advantages and limitations of the three RaPID-magnetic particle-based ELISA kits applied to the characterization of industrial effluents are also reported.

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

    PubMed

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

    2015-09-01

    Although the coupling of GC/MS with atmospheric pressure ionization (API) has been reported in 1970s, the interest in coupling GC with atmospheric pressure ion source was expanded in the last decade. The demand of a "soft" ion source for preserving highly diagnostic molecular ion is desirable, as compared to the "hard" ionization technique such as electron ionization (EI) in traditional GC/MS, which fragments the molecule in an extensive way. These API sources include atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), atmospheric pressure laser ionization (APLI), electrospray ionization (ESI) and low temperature plasma (LTP). This review discusses the advantages and drawbacks of this analytical platform. After an introduction in atmospheric pressure ionization the review gives an overview about the history and explains the mechanisms of various atmospheric pressure ionization techniques used in combination with GC such as APCI, APPI, APLI, ESI and LTP. Also new developments made in ion source geometry, ion source miniaturization and multipurpose ion source constructions are discussed and a comparison between GC-FID, GC-EI-MS and GC-API-MS shows the advantages and drawbacks of these techniques. The review ends with an overview of applications realized with GC-API-MS. PMID:26388363

  14. 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

  15. Gas chromatography/atmospheric pressure chemical ionization/mass spectrometry for the analysis of organochlorine pesticides and polychlorinated biphenyls in human serum.

    PubMed

    Geng, Dawei; Jogsten, Ingrid Ericson; Dunstan, Jody; Hagberg, Jessika; Wang, Thanh; Ruzzin, Jerome; Rabasa-Lhoret, Rémi; van Bavel, Bert

    2016-07-01

    A method using a novel atmospheric pressure chemical ionization source for coupling gas chromatography (GC/APCI) to triple quadrupole mass spectrometry (MS/MS) for the determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) regulated by the Stockholm Convention is presented. One microliter injection of a six-point calibration curve of native PCBs and OCPs, ranging from 0.04 to 300pg/μL, was performed. The relative standard deviation (RSD) of the relative response factors (RRFs) was less than 15% with a coefficient of determination (r(2))>0.995. Meanwhile, two calibration solutions (CS), CS 2 (0.4pg/μL) and CS 3 (4pg/μL) were analyzed to study the repeatability calculated for both area and RRFs. The RSD for RRF ranged from 3.1 to 16% and 3.6 to 5.5% for CS 2 and CS 3, respectively. The limits of detection (LOD) determined by peak-to-peak signal-to-noise ratio (S/N) of 3 were compared between the GC/APCI/MS/MS and a GC coupled to high resolution mass spectrometry (GC/HRMS) system. GC/APCI/MS/MS resulted in lower LOD for most of the compounds, except for PCB#74, cis-chlordane and trans-chlordane. GC/APCI/MS/MS and GC/HRMS were also compared by performing analysis on 75 human serum samples together with eight QA/QC serum samples. The comparison between GC/APCI/MS/MS system and GC/HRMS system for 16 of the targeted compounds was carried out. No statistically significant difference was discovered. Due to increased sensitivity and user friendly operation under atmospheric pressure, GC/APCI/MS/MS is a powerful alternative technique that can easily meet the specification of GC/HRMS. PMID:27236485

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

    PubMed

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

    2015-07-24

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

  17. Potential of atmospheric pressure chemical ionization source in gas chromatography tandem mass spectrometry for the screening of urinary exogenous androgenic anabolic steroids.

    PubMed

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

    2016-02-01

    The atmospheric pressure chemical ionization (APCI) source for gas chromatography-mass spectrometry analysis has been evaluated for the screening of 16 exogenous androgenic anabolic steroids (AAS) in urine. The sample treatment is based on the strategy currently applied in doping control laboratories i.e. enzymatic hydrolysis, liquid-liquid extraction (LLE) and derivatization to form the trimethylsilyl ether-trimethylsilyl enol ether (TMS) derivatives. These TMS derivatives are then analyzed by gas chromatography tandem mass spectrometry using a triple quadrupole instrument (GC-QqQ MS/MS) under selected reaction monitoring (SRM) mode. The APCI promotes soft ionization with very little fragmentation resulting, in most cases, in abundant [M + H](+) or [M + H-2TMSOH](+) ions, which can be chosen as precursor ions for the SRM transitions, improving in this way the selectivity and sensitivity of the method. Specificity of the transitions is also of great relevance, as the presence of endogenous compounds can affect the measurements when using the most abundant ions. The method has been qualitatively validated by spiking six different urine samples at two concentration levels each. Precision was generally satisfactory with RSD values below 25 and 15% at the low and high concentration level, respectively. Most the limits of detection (LOD) were below 0.5 ng mL(-1). Validation results were compared with the commonly used method based on the electron ionization (EI) source. EI analysis was found to be slightly more repeatable whereas lower LODs were found for APCI. In addition, the applicability of the developed method has been tested in samples collected after the administration of 4-chloromethandienone. The highest sensitivity of the APCI method for this compound, allowed to increase the period in which its administration can be detected. PMID:26772132

  18. Gas chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization for fluorotelomer alcohols and perfluorinated sulfonamides determination.

    PubMed

    Portolés, Tania; Rosales, Luis E; Sancho, Juan V; Santos, F Javier; Moyano, Encarnación

    2015-09-25

    Ionization and in source-fragmentation behavior of four fluorotelomer alcohols (FTOH) (4:2 FTOH, 6:2 FTOH, 8:2 FTOH and 10:2 FTOH) and four N-alkyl fluorooctane sulfonamides/-ethanols (N-MeFOSA, N-EtFOSA, N-MeFOSE and N-EtFOSE) by APCI has been studied and compared with the traditionally used EI and CI. Protonated molecule was the base peak of the APCI spectrum in all cases giving the possibility of selecting it as a precursor ion for MS/MS experiments. Following, CID fragmentation showed common product ions for all FOSAs/FOSEs (C4F7 and C3F5). Nevertheless, the different functionality gave characteristic pattern fragmentations. For instance, FTOHs mainly loss H2O+HF, FOSAs showed the losses of SO2 and HF while FOSEs showed the losses of H2O and SO2. Linearity, repeatability and LODs have been studied obtaining instrumental LODs between 1 and 5fg. Finally, application to river water and influent and effluent waste water samples has been carried out in order to investigate the improvements in detection capabilities of this new source in comparison with the traditionally used EI/CI sources. Matrix effects in APCI have been evaluated in terms of signal enhancement/suppression when comparing standards in solvent and matrix. No matrix effects were observed and concentrations found in samples were in the range of 1-100pgL(-1) far below the LODs achieved with methods previously reported. Unknown related perfluoroalkyl substances, as methyl-sulfone and methyl-sulfoxide analogues for FTOHs, were also discovered and tentatively identified. PMID:26298605

  19. Screening of pesticides and polycyclic aromatic hydrocarbons in feeds and fish tissues by gas chromatography coupled to high-resolution mass spectrometry using atmospheric pressure chemical ionization.

    PubMed

    Nácher-Mestre, Jaime; Serrano, Roque; Portolés, Tania; Berntssen, Marc H G; Pérez-Sánchez, Jaume; Hernández, Félix

    2014-03-12

    This paper reports a wide-scope screening for detection and identification of pesticides and polycyclic aromatic hydrocarbons (PAHs) in feeds and fish tissues. QuEChERS sample treatment was applied, using freezing as an additional cleanup. Analysis was carried out by gas chromatography coupled to hybrid quadrupole time-of-flight mass spectrometry with atmospheric pressure chemical ionization (GC-(APCI) QTOF MS). The qualitative validation was performed for over 133 representative pesticides and 24 PAHs at 0.01 and 0.05 mg/kg. Subsequent application of the screening method to aquaculture samples made it possible to detect several compounds from the target list, such as chlorpyrifos-methyl, pirimiphos-methyl, and ethoxyquin, among others. Light PAHs (≤4 rings) were found in both animal and vegetable samples. The reliable identification of the compounds was supported by accurate mass measurements and the presence of at least two representative m/z ions in the spectrum together with the retention time of the peak, in agreement with the reference standard. Additionally, the search was widened to include other pesticides for which standards were not available, thanks to the expected presence of the protonated molecule and/or molecular ion in the APCI spectra. This could allow the detection and tentative identification of other pesticides different from those included in the validated target list. PMID:24559176

  20. Application of pentafluorophenyl hydrazine derivatives to the analysis of nabumetone and testosterone in human plasma by liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Sheen, J F; Her, G R

    2004-12-01

    Two carbonyl compounds, nabumetone and testosterone, were derivatized with pentafluorophenyl hydrazine (PFPH) and analyzed by atmospheric-pressure chemical-ionization mass spectrometry. The PFPH derivatives underwent dissociative electron capture in negative-ion APCI (ECAPCI) and gave intense [M-20](-) ions in the mass spectra. In positive-ion APCI, the PFPH derivatives underwent efficient protonation and gave intense [M + H](+) ions in the mass spectra. In CID, the major product ions of the [M-20](-) ions in ECAPCI corresponded to the partial moiety of PFPH. In contrast, the major product ions of [M + H](+) corresponded to the partial moiety of the analyte. By using selected reaction monitoring (SRM) detection, low pg of nabumetone (1 pg) and testosterone (7 pg) could be detected in both ECAPCI and positive-ion APCI. In comparison with the detection limits (SRM) of the underivatized analytes, use of the PFPH derivatives resulted in 2500-fold and 35-fold sensitivity enhancements for nabumetone and testosterone, respectively. The PFPH derivatives were applied to the analysis of nabumetone and testosterone in human plasma by both ECAPCI and positive-ion APCI and were found to enable detection of 0.1 ng mL(-1) nabumetone in spiked plasma. For testosterone, endogenous testosterone in female plasma was detected in both ECAPCI and positive-ion APCI. PMID:15700167

  1. High-throughput trace analysis of explosives in water by laser diode thermal desorption/atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Badjagbo, Koffi; Sauvé, Sébastien

    2012-07-01

    Harmful explosives can accumulate in natural waters in the long term during their testing, usage, storage, and dumping and can pose a health risk to humans and the environment. For the first time, attachment of small anions to neutral molecules in laser diode thermal desorption/atmospheric pressure chemical ionization was systematically investigated for the direct determination of trace nitroaromatics, nitrate esters, and nitramine explosives in water. Using ammonium chloride as an additive improved the instrument response for all the explosives tested and promoted the formation of several characteristic adduct ions. The method performs well achieving good linearity over at least 2 orders of magnitude, with coefficients of determination greater than 0.995. The resulting limits of detection are in the range of 0.009-0.092 μg/L. River water samples were successfully analyzed by the proposed method with accuracy in the range of 96-98% and a response time of 15 s, without any further pretreatment or chromatographic separation. PMID:22746321

  2. 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

  3. Continuous water infusion enhances atmospheric pressure chemical ionization of methyl chloroformate derivatives in gas chromatography coupled to time-of-flight mass spectrometry-based metabolomics.

    PubMed

    Wachsmuth, Christian J; Dettmer, Katja; Lang, Sven A; Mycielska, Maria E; Oefner, Peter J

    2014-09-16

    The effects of continuous water infusion on efficiency and repeatability of atmospheric pressure chemical ionization of both methyl chloroformate (MCF) and methoxime-trimethylsilyl (MO-TMS) derivatives of metabolites were evaluated using gas chromatography-time-of-flight mass spectrometry. Water infusion at a flow-rate of 0.4 mL/h yielded not only an average 16.6-fold increase in intensity of the quasimolecular ion for 20 MCF-derivatized metabolite standards through suppression of in-source fragmentation but also the most repeatable peak area integrals. The impact of water infusion was the greatest for dicarboxylic acids and the least for (hetero-) aromatic compounds. Water infusion also improved the ability to detect reliably fold changes as small as 1.33-fold for the same 20 MCF-derivatized metabolite standards spiked into a human serum extract. On the other hand, MO-TMS derivatives were not significantly affected by water infusion, neither in their fragmentation patterns nor with regard to the detection of differentially regulated compounds. As a proof of principle, we applied MCF derivatization and GC-APCI-TOFMS to the detection of changes in abundance of metabolites in pancreatic cancer cells upon treatment with 17-DMAG. Water infusion increased not only the number of metabolites identified via their quasimolecular ion but also the reproducibility of peak areas, thereby almost doubling the number of significantly regulated metabolites (false discovery rate < 0.05) to a total of 23. PMID:25152309

  4. Characterization of gamma-irradiated polyethylene terephthalate by liquid-chromatography mass-spectrometry (LC MS) with atmospheric-pressure chemical ionization (APCI)

    NASA Astrophysics Data System (ADS)

    Buchalla, Rainer; Begley, Timothy H.

    2006-01-01

    Low-molecular-weight (low-MW) constituents of polyethylene terephthalate (PET), irradiated with 60Co gamma rays at 25 and 50 kGy, were analyzed by HPLC-MS with atmospheric-pressure chemical ionization (APCI). Consistent with earlier results, the concentrations of the major compounds that are present in the non-irradiated PET do not change perceptibly. However, we find a small but significant increase in terephthalic acid ethylester, from less than 1 mg/kg in the non-irradiated control to ca. 2 mg/kg after 50 kGy, which has not been described before. The finding is important because it gives an impression of the sensitivity of the analytical method. Additionally, it shows that even very radiation-resistant polymers can form measurable amounts of low-MW radiolysis products. The potential and limitations of LC-MS for the analysis of radiolysis products and unidentified migrants are briefly discussed in the context of the question: How can we validate our analytical methods for unknown analytes?

  5. Quantitation of the 5HT1D agonists MK-462 and sumatriptan in plasma by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    McLoughlin, D A; Olah, T V; Ellis, J D; Gilbert, J D; Halpin, R A

    1996-03-01

    The 5HT1D agonist sumatriptan is efficacious in the treatment of migraines. MK-462 is a drug of the same class which is under development in our laboratories. Bioanalytical methods of high efficiency, specificity and sensitivity were required to support the preclinical and clinical programs. These assays were based on HPLC with tandem MS-MS detection. MK-462 and sumatriptan were extracted using an automated solid-phase extraction technique on a C2 Varian Bond-Elut cartridge. The n-diethyl analogues of MK-462 and sumatriptan were used as internal standards. The analytes were chromatographed using reversed-phase (nitrile) columns coupled via a heated nebulizer interface to an atmospheric pressure chemical ionization source. The chromatographic run times were less than 7 min. Both methods were precise, accurate and selective down to plasma concentrations of 0.5 ng/ml. The assay for MK-462 was adapted to separately monitor the unlabeled and 14C-labeled species of the drug following intravenous administration of radiolabeled material to man. PMID:8900521

  6. Determination of aldicarb, aldicarb sulfoxide and aldicarb sulfone in some fruits and vegetables using high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Nunes, G S; Alonso, R M; Ribeiro, M L; Barceló, D

    2000-08-01

    An analytical method for the determination of aldicarb, and its two major metabolites, aldicarb sulfoxide and aldicarb sulfone in fruits and vegetables is described. Briefly the method consisted of the use of a methanolic extraction, liquid-liquid extraction followed by solid-phase extraction clean-up. Afterwards, the final extract is analyzed by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS). The specific fragment ion corresponding to [M-74]+ and the protonated molecular [M+H]+ ion were used for the unequivocal determination of aldicarb and its two major metabolites. The analytical performance of the proposed method and the results achieved were compared with those obtained using the common analytical method involving LC with post-column fluorescence detection (FL). The limits of detection varied between 0.2 and 1.3 ng but under LC-FL were slightly lower than when using LC-APCI-MS. However both methods permitted one to achieve the desired sensitivity for analyzing aldicarb and its metabolites in vegetables. The method developed in this work was applied to the trace determination of aldicarb and its metabolites in crop and orange extracts. PMID:10949478

  7. Determination of the mycotoxin moniliformin in cultures of Fusarium subglutinans and in naturally contaminated maize by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Sewram, V; Nieuwoudt, T W; Marasas, W F; Shephard, G S; Ritieni, A

    1999-07-01

    A LC-MS method employing triethylamine as ion-pairing reagent for the determination of moniliformin in culture material and naturally contaminated maize samples is described. Mass spectrometric detection of moniliformin was accomplished following atmospheric pressure chemical ionization to yield the deprotonated molecular ion [M-H]- at m/z 97. The moniliformin response was found to be linear over the injected range 10 ng to 700 ng and a detection limit of 10 ng was attainable at a signal-to-noise (S/N) ratio of 4. Five South African strains of Fusarium subglutinans were grown on maize kernels and moniliformin extracted with an acetonitrile-water (95:5) mixture. Following sample clean up with reversed-phase (C18) solid-phase extraction cartridges, the extracts were subjected to LC-MS analysis. Triethylamine was used as an ion-pair reagent and found to improve the retention characteristics of moniliformin without any detrimental effects to the instrument. Moniliformin concentrations ranged between 130 mg/kg and 1460 mg/kg culture. Application of this method to naturally contaminated maize samples from Transkei showed that it was capable of measuring moniliformin levels down to 10 micrograms/kg in selected moldy maize cobs. This is the first report on the application of LC-MS to the analysis of moniliformin in cultures of F. subglutinans and in naturally contaminated maize. PMID:10427758

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

    PubMed

    Háková, Eva; Vrkoslav, Vladimír; Míková, Radka; Schwarzová-Pecková, Karolina; Bosáková, Zuzana; Cvačka, Josef

    2015-07-01

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

  9. Analysis of vitamin K1 in fruits and vegetables using accelerated solvent extraction and liquid chromatography tandem mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Jäpelt, Rie Bak; Jakobsen, Jette

    2016-02-01

    The objective of this study was to develop a rapid, sensitive, and specific analytical method to study vitamin K1 in fruits and vegetables. Accelerated solvent extraction and solid phase extraction was used for sample preparation. Quantification was done by liquid chromatography tandem mass spectrometry with atmospheric pressure chemical ionization in selected reaction monitoring mode with deuterium-labeled vitamin K1 as an internal standard. The precision was estimated as the pooled estimate of three replicates performed on three different days for spinach, peas, apples, banana, and beetroot. The repeatability was 5.2% and the internal reproducibility was 6.2%. Recovery was in the range 90-120%. No significant difference was observed between the results obtained by the present method and by a method using the same principle as the CEN-standard i.e. liquid-liquid extraction and post-column zinc reduction with fluorescence detection. Limit of quantification was estimated to 0.05 μg/100g fresh weight. PMID:26304366

  10. Total Analysis of Microcystins in Fish Tissue Using Laser Thermal Desorption-Atmospheric Pressure Chemical Ionization-High-Resolution Mass Spectrometry (LDTD-APCI-HRMS).

    PubMed

    Roy-Lachapelle, Audrey; Solliec, Morgan; Sinotte, Marc; Deblois, Christian; Sauvé, Sébastien

    2015-08-26

    Microcystins (MCs) are cyanobacterial toxins encountered in aquatic environments worldwide. Over 100 MC variants have been identified and have the capacity to covalently bind to animal tissue. This study presents a new approach for cell-bound and free microcystin analysis in fish tissue using sodium hydroxide as a digestion agent and Lemieux oxidation to obtain the 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) moiety, common to all microcystin congeners. The use of laser diode thermal desorption-atmospheric pressure chemical ionization coupled with Q-Exactive mass spectrometry (LDTD-APCI-HRMS) led to an analysis time of approximately 10 s per sample and high-resolution detection. Digestion/oxidation and solid phase extraction recoveries ranged from 70 to 75% and from 86 to 103%, respectively. Method detection and quantification limits values were 2.7 and 8.2 μg kg(-1), respectively. Fish samples from cyanobacteria-contaminated lakes were analyzed, and concentrations ranging from 2.9 to 13.2 μg kg(-1) were reported. PMID:26211936

  11. Trace determination of 1-aminopropanone, a potential marker for wastewater contamination by liquid chromatography and atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Singh, Simrat P; Gardinali, Piero R

    2006-02-01

    1-Aminopropanone (APR) is a volatile aminoketone of human origin that has been identified in raw sewage and surface waters. However, the traditional methodology for the determination of APR is extremely complicated and requires a skilled chemist to achieve consistent results. This investigation presents a novel and simple method for the analysis of APR by direct derivatization in aqueous media. APR is synthesized as its hydrochloride and derivatized using mercaptoethanol and o-phthalaldehyde. The product of reaction is separated on a 15 cm x 4.6 mm Luna C-18 column (1 mL/min, 45:55 acetonitrile: Water) and detected using a single quadrupole mass spectrometer detector operated in atmospheric pressure chemical ionization (APCI) mode. Method detection limits as low as 100 nM were routinely obtained with a precision of 1.7%. Recoveries of APR were always found to be greater then 88% in surface and wastewater samples fortified at three different levels. However, despite the robustness of the method and the fact that APR was consistently detected in urine it was not present in a variety surface or wastewaters analyzed during the course of the study. These results pose a critical question on the use of APR as a tracer for human derived wastewaters. PMID:16443254

  12. Determination of talinolol in human plasma using automated on-line solid phase extraction combined with atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

    Bourgogne, Emmanuel; Grivet, Chantal; Hopfgartner, Gérard

    2005-06-01

    A specific LC-MS/MS assay was developed for the automated determination of talinolol in human plasma, using on-line solid phase extraction system (prospekt 2) combined with atmospheric pressure chemical ionization (APCI) tandem mass spectrometry. The method involved simple precipitation of plasma proteins with perchloric acid (contained propranolol) as the internal standard (IS) and injection of the supernatant onto a C8 End Capped (10 mmx2 mm) cartridge without any evaporation step. Using the back-flush mode, the analytes were transferred onto an analytical column (XTerra C18, 50 mmx4.6 mm) for chromatographic separation and mass spectrometry detection. One of the particularities of the assay is that the SPE cartridge is used as a column switching device and not as an SPE cartridge. Therefore, the same SPE cartridge could be used more than 28 times, significantly reducing the analysis cost. APCI ionization was selected to overcome any potential matrix suppression effects because the analyte and IS co-eluted. The mean precision and accuracy in the concentration range 2.5-200 ng/mL was found to be 103% and 7.4%, respectively. The data was assessed from QC samples during the validation phase of the assay. The lower limit of quantification was 2.5 ng/mL, using a 250 microL plasma aliquot. The LC-MS/MS method provided the requisite selectivity, sensitivity, robustness accuracy and precision to assess pharmacokinetics of the compound in several hundred human plasma samples. PMID:15866498

  13. 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 (α-pinene and Δ3-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

  14. 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 (α-pinene and Δ3-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.

  15. Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Portolés, T; Mol, J G J; Sancho, J V; López, Francisco J; Hernández, F

    2014-08-01

    A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target acquisition was performed through two alternating scan events: one at low collision energy and another at a higher collision energy ramp (MS(E)). In this way, both protonated molecule and/or molecular ion together with fragment ions were obtained in a single run. Validation was performed according to SANCO/12571/2013 by analysing 20 samples (10 different commodities in duplicate), fortified with a test set of 132 pesticides at 0.01, 0.05 and 0.20mg kg(-1). For screening, the detection was based on one diagnostic ion (in most cases the protonated molecule). Overall, at the 0.01mg kg(-1) level, 89% of the 2620 fortifications made were detected. The screening detection limit for individual pesticides was 0.01mg kg(-1) for 77% of the pesticides investigated. The possibilities for identification according to the SANCO criteria, requiring two ions with a mass accuracy ≤±5ppm and an ion-ratio deviation ≤±30%, were investigated. At the 0.01mg kg(-1) level, identification was possible for 70% of the pesticides detected during screening. This increased to 87% and 93% at the 0.05 and 0.20mg kg(-1) level, respectively. Insufficient sensitivity for the second ion was the main reason for the inability to identify detected pesticides, followed by deviations in mass accuracy and ion ratios. PMID:25064246

  16. A high-performance liquid chromatographic-atmospheric pressure chemical ionization-tandem mass spectrometric method for determination of risperidone and 9-hydroxyrisperidone in human plasma.

    PubMed

    Moody, David E; Laycock, John D; Huang, Wei; Foltz, Rodger L

    2004-09-01

    Risperidone, a benzisoxazole derivative, is an antipsychotic agent used for the treatment of schizophrenia. We developed a liquid chromatographic-atmospheric pressure chemical ionization-tandem mass spectrometric (LC-APCI-MS-MS) method with improved sensitivity, selectivity, and dynamic range for determination of risperidone and 9-hydroxyrisperidone in human plasma. A structural analogue of risperidone, RO68808 (5 ng/mL), is added as the internal standard to 1 mL of human plasma. Plasma is made basic, extracted with pentane/methylene chloride (3:1), the organic phase evaporated to dryness, and the residue is reconstituted in water with 0.1% formic acid/acetonitrile (20:1). For LC-MS-MS analysis, a Metachem Inertsel HPLC column (2.1 x 150 mm, 5-microm particle size) is connected to a Finnigan TSQ7000 tandem MS via the Finnigan API interface. Both electrospray (ESI) and APCI produced predominantly MH(+) ions for the two analytes and the internal standard. Ions detected by selected reaction monitoring correspond to the following transitions: m/z 411 to 191 for risperidone, m/z 427 to 207 for 9-hydroxyrisperidone, and m/z 421 to 201 for the internal standard. APCI provided a larger dynamic range (0.1 to 25 ng/mL) and better precision and accuracy than ESI. Intrarun accuracy and precision determined at 0.1, 0.25, 2.5, and 15 ng/mL were within 12% of target with %CVs not exceeding 10.9%. Interrun accuracy and precision determined at the same concentrations were within 9.6% of target with %CVs not exceeding 6.7%. Analytes were stable in plasma after 24 h at room temperature, 2 freeze-thaw cycles, and 490 days at -20 degrees C. PMID:15516302

  17. Determination and differentiation of triacylglycerol molecular species in Antarctic and non-Antarctic yeasts by atmospheric pressure-chemical ionization-mass spectrometry.

    PubMed

    Bhuiyan, Mohammad; Tucker, David; Watson, Kenneth

    2013-09-01

    Yeast, particularly Saccharomyces cerevisiae, has long served as a model eukaryotic system for studies on the regulation of lipid metabolism. We developed a high performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry method for the detailed analysis of triacylglycerols (TAGs) in 14 species of yeast consisting of seven Antarctic yeasts (grown at 15°C and 5°C) and seven non-Antarctic yeasts (grown at 25°C and 15°C), the latter including 3 strains of S. cerevisiae. Analysis of TAG molecular species established that the sn-2 position was invariably occupied by an unsaturated fatty acyl moiety. In S. cerevisiae the preference was for oleic acid 18:1>palmitoleic acid 16:1, in Candida albicans, Cryptococcus humicolus and Rhodotorula mucilaginosa 18:1>linoleic acid 18:2 and in Zygosaccharomyces rouxii 18:2>18:1. In the Antarctic yeasts (Cryptococcus watticus, Cryptococcus victoriae, Cryptococcus nyarrowii, Leucosporidium antarcticum, Leucosporidium fellii, Candida psychrophila and Rhodotorula mucilaginosa) the general pattern was for the sn-2 position to be occupied by 18:1, 18:2 or linolenic acid 18:3. A trend towards synthesis of increased unsaturated fatty acid in TAGs was observed as the growth temperature was lowered. The application of principal component analysis demonstrated that the yeasts were differentiated into three distinct groups. One group consisted of the three S. cerevisiae strains, a second the other four non-Antarctic yeasts and the third the seven Antarctic yeasts. The data for the Antarctic yeasts, to the best of our knowledge, have not been previously reported. PMID:23831436

  18. Separation and determination of diversiform phytosterols in food materials using supercritical carbon dioxide extraction and ultraperformance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Lu, Baiyi; Zhang, Ying; Wu, Xiaoqin; Shi, Jiayi

    2007-04-01

    This paper presents at first time that the ultra-performance liquid chromatographic atmospheric pressure chemical ionization mass spectrometer (UPLC-APCI-MS) was used as an efficient method for the identification and quantification of diversiform phytosterols in food materials. The sample preparation consisted of extraction by supercritical carbon dioxide fluid extraction (SCE) and saponification by refluxing with ethanolic KOH, and then the non-saponificable fraction was extracted with petroleum ether. This fraction was subjected to solid phase extraction (SPE) on silica gel cartridge and then the sterols were eluted with hexane-ethyl acetate. Sterols were separated on an Acquity UPLC BEH C18 column (100 mm x 1.0 mm, 1.7 microm particle size) with a gradient of methanol/water (1% acetonitrile) at a flow of 0.1 mL min(-1). The determination was performed in selective ion monitoring mode. The quality parameter of the developed method was established using 6-ketocholestanol as internal standard. Limits of quantification (LOQ) were 0.1754, 0.0341, 0.0500, 0.0205, 0.0225, 0.3674, 0.0241, 0.0272, 0.0076 microg L(-1) and 0.1525 microg mL(-1) for 6-ketocholestanol, desmosterol, ergosterol, cholesterol, lanosterol, cholestanol, campesterol, stigmasterol, beta-sitosterol, and stigmastanol, respectively. The intra- and inter-day determination precision for the 10 phytosterols were less than 5 and 6% in relative standard deviations, and their recoveries were located in the range of 94-107%. The developed approach has been applied successfully for efficient determination of diversiform phytosterols in food materials, including corn, sesame, oat and peanut. PMID:17386793

  19. Determination of 21-hydroxydeflazacort in human plasma by high-performance liquid chromatography/atmospheric pressure chemical ionization tandem mass spectrometry. Application to bioequivalence study.

    PubMed

    Ifa, D R; Moraes, M E; Moraes, M O; Santagada, V; Caliendo, G; de Nucci, G

    2000-03-01

    A liquid chromatographic atmospheric pressure chemical ionization tandem mass spectrometric method is described for the determination of 21-hydroxydeflazacort in human plasma using dexamethasone 21-acetate as an internal standard. The procedure requires a single diethyl ether extraction. After evaporation of the solvent under a nitrogen flow, the analytes are reconstituted in the mobile phase, chromatographed on a C18 reversed-phase column and analyzed by mass spectrometry via a heated nebulizer interface where they are detected by multiple reaction monitoring. The method has a chromatographic run time of less than 5 min and a linear calibration curve with a range of 1-400 ng ml(-1) (r>0.999). The between-run precision, based on the relative standard deviation for replicate quality controls, was < or =5.5% (10 ng ml(-1)), 1.0% (50 ng ml(-1)) and 2.7% (200 ng ml(-1)). The between-run accuracy was +/-7.1, 3.8 and 4.8% for the above concentrations, respectively. This method was employed in a bioequivalence study of two DFZ tablet formulations (Denacen from Marjan Industria e Comercio, Brazil, as a test formulation, and Calcort from Merrell Lepetit, Brazil, as a reference formulation) in 24 healthy volunteers of both sexes who received a single 30 mg dose of each formulation. The study was conducted using an open, randomized, two-period crossover design with a 7-day washout interval. The 90% confidence interval (CI) of the individual geometric mean ratio for Denacen/Calcort was 89.8-109.5% for area under the curve AUC(0-24 h) and 80.7-98.5% for Cmax. Since both the 90% CI for AUC(0-24 h) and Cmax were included in the 80-125% interval proposed by the US Food and Drug Administration, Denacen was considered bioequivalent to Calcort according to both the rate and extent of absorption. PMID:10767775

  20. In-Line Ozonation for Sensitive Air-Monitoring of a Mustard-Gas Simulant by Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Okumura, Akihiko

    2015-09-01

    A highly sensitive method for real-time air-monitoring of mustard gas (bis(2-chloroethyl) sulfide, HD), which is a lethal blister agent, is proposed. Humidified air containing a HD simulant, 2-chloroethyl ethyl sulfide (2CEES), was mixed with ozone and then analyzed by using an atmospheric pressure chemical ionization ion trap tandem mass spectrometer. Mass-spectral ion peaks attributable to protonated molecules of intact, monooxygenated, and dioxygenated 2CEES (MH+, MOH+, and MO2H+, respectively) were observed. As ozone concentration was increased from zero to 30 ppm, the signal intensity of MH+ sharply decreased, that of MOH+ increased once and then decreased, and that of MO2H+ sharply increased until reaching a plateau. The signal intensity of MO2H+ at the plateau was 40 times higher than that of MH+ and 100 times higher than that of MOH+ in the case without in-line ozonation. Twenty-ppm ozone gas was adequate to give a linear calibration curve for 2CEES obtained by detecting the MO2H+ signal in the concentration range up to 60 μg/m3, which is high enough for hygiene management. In the low concentration range lower than 3 μg/m3, which is equal to the short-term exposure limit for HD, calibration plots unexpectedly fell off the linear calibration curve, but 0.6-μg/m3 vapor was actually detected with the signal-to-noise ratio of nine. Ozone was generated from instrumentation air by using a simple and inexpensive home-made generator. 2CEES was ozonated in 1-m extended sampling tube in only 1 s.

  1. Use of liquid chromatography-atmospheric pressure chemical ionization-ion trap mass spectrometry for identification of oleanolic acid and ursolic acid in Anoectochilus roxburghii (wall.) Lindl.

    PubMed

    Huang, Liying; Chen, Tianwen; Ye, Zhao; Chen, Guonan

    2007-07-01

    Oleanolic acid (OA) and ursolic acid (UA) are the two important bioactive compounds in Anoectochilus roxburghii (wall) Lindl (A. roxburghii), which has been used as a traditional Chinese medicine. So far, there has been no report to indicate that A. roxburghii contains these two bioactive compounds. It is necessary to develop an effective method to extract and analyze OA and UA in A. roxburghii. In this paper, a quantitative method, consisting of supercritical fluid extraction (SFE) followed by liquid chromatography-atmospheric pressure chemical ionization-ion trap mass spectrometry (LC-APCI-IT-MS) analysis, was developed for identification of OA and UA in A. roxburghii. The extraction was carried out by using CO(2) as the supercritical fluid and ethanol as the modifier before LC separation. The mobile phase used for LC separation consisted of acetic acid (1%, v/v), water (15%, v/v) and methanol (84%, v/v), and the elution was performed at a flow rate of 0.8 ml/min. The mass spectrometer was operated in APCI(+) mode with selected ion monitoring (SIM) to quantify OA and UA at m/z 439.4. Under optimum conditions, the linear responses of OA and UA were obtained in the concentration range of 0.5-80 (r = 0.9992) and 0.5-50 microg/ml (r = 0.9989) with the detection limits of 0.125 and 0.085 microg/ml, respectively. The proposed method has been used for the identification and quantitation of OA and UA in a real A. roxburghii sample. PMID:17535010

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

    PubMed

    Solliec, Morgan; Massé, Daniel; Sauvé, Sébastien

    2014-10-01

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

  3. Identification of Organic Nitrates in the NO3 Radical Initiated Oxidation of α-Pinene by Atmospheric Pressure Chemical Ionization Mass Spectrometry

    SciTech Connect

    Perraud, Veronique M.; Bruns, Emily A.; Ezell, Michael J.; Johnson, Stanley N.; Greaves, John; Finlayson-Pitts, Barbara J.

    2010-07-07

    The gas-phase reactions of nitrate radicals (NO3) with biogenic organic compounds are a major sink for these organics during night-time. These reactions form secondary organic aerosols, including organic nitrates that can undergo long-range transport, releasing NOx downwind. We report here studies of the reaction of NO3 with R-pinene at 1 atm in dry synthetic air(relative humidity ~3%) and at 298K using atmospheric pressure chemical ionization triple quadrupole mass spectrometry (APCI-MS) to identify gaseous and particulate products. The emphasis is on the identification of individual organic nitrates in the particle phase that were obtained by passing the product mixture through a denuder to remove gas-phase reactants and products prior to entering the source region of the mass spectrometer. Filter extracts were also analyzed by GCMS and by APCI time-of-flight mass spectrometry (APCI-ToFMS) with methanol as the proton source. In addition to pinonaldehyde and pinonic acid, five organic nitrates were identified in the particles as well as in the gas phase: 3-oxopinane- 2-nitrate, 2-hydroxypinane-3-nitrate, pinonaldehyde-PAN, norpinonaldehyde-PAN, and (3-acetyl-2,2-dimethyl-3-nitrooxycyclobutyl) acetaldehyde. Furthermore, there was an additional first generation organic nitrate product tentatively identified as a carbonyl hydroxynitrate with a molecular mass of 229. These studies suggest that a variety of organic nitrates would partition between the gas phase and particles in the atmosphere, and serve as a reservoir for NOx.

  4. Use of electron ionization and atmospheric pressure chemical ionization in gas chromatography coupled to time-of-flight mass spectrometry for screening and identification of organic pollutants in waters.

    PubMed

    Portolés, Tania; Mol, Johannes G J; Sancho, Juan V; Hernández, Félix

    2014-04-25

    A new approach has been developed for multiclass screening of organic contaminants in water based on the use of gas chromatography coupled to hybrid quadrupole high-resolution time-of-flight mass spectrometry with atmospheric pressure chemical ionization (GC-(APCI)QTOF MS). The soft ionization promoted by the APCI source allows effective and wide-scope screening based on the investigation of the molecular ion and/or protonated molecule. This is in contrast to electron ionization (EI) where ionization typically results in extensive fragmentation, and diagnostic ions and/or spectra need to be known a priori to facilitate detection of the analytes in the raw data. Around 170 organic contaminants from different chemical families were initially investigated by both approaches, i.e. GC-(EI)TOF and GC-(APCI)QTOF, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and a notable number of pesticides and relevant metabolites. The new GC-(APCI)QTOF MS approach easily allowed widening the number of compounds investigated (85 additional compounds), with more pesticides, personal care products (UV filters, musks), polychloronaphthalenes (PCNs), antimicrobials, insect repellents, etc., most of them considered as emerging contaminants. Both GC-(EI)TOF and GC-(APCI)QTOF methodologies have been applied, evaluating their potential for a wide-scope screening in the environmental field. PMID:24674644

  5. Determination of benzoylurea insecticide residues in tomatoes by high-performance liquid chromatography with ultraviolet-diode array and atmospheric pressure chemical ionization-mass spectrometry detection.

    PubMed

    Markoglou, Anastasios N; Bempelou, Eleftheria D; Liapis, Konstantinos S; Ziogas, Basil N

    2007-01-01

    A simple and sensitive method using high-performance liquid chromatography/ mass spectrometry (LC/MS) was developed and validated for simultaneous determination of 5 benzoylurea insecticides-diflubenzuron, triflumuron, teflubenzuron, lufenuron, and flufenoxuron-in tomatoes. Residues were successfully separated on a C18 column by methanol-water isocratic elution. Detection was carried out by an ultraviolet diode array detector (UV-DAD) coupled with a quadrupole mass spectrometer, using atmospheric pressure chemical ionization (APCI) in negative-ion mode. The main ions were the deprotonated molecules [M-H]- for triflumuron, and the anions formed by elimination of hydrofluoric acid [M-H-HF]- for diflubenzuron and flufenoxuron, and [M-2H-HF] for lufenuron and teflubenzuron. The calibration plots were linear for both detectors over the range 0.05 to 10 microg/mL, and the method presented good quality parameters. The limits of detection for standard solutions were 0.008-0.01 mg/L (equivalent to 0.08-0.1 ng injected) for both detectors, and the limits of quantification (LOQs) were approximately 10 times lower than national maximum residue levels (MRLs). Depending on the compound and the detector, the LOQ values ranged from 0.2 to 0.4 ng injected. The optimum LC-UV-DAD/APCI-MS conditions were applied to the analysis of benzoylureas in tomatoes. The obtained recoveries from fortified tomato samples (50 g), extracted with ethyl acetate and purified by solid-phase extraction on silica sorbent, were 88-100 and 92.9-105% for the UV-DAD and MS detectors, respectively, with precision values (relative standard deviations) of 2.9-11 and 3.7-14%, respectively. The method was applied to 12 tomato samples from local markets, and diflubenzuron and lufenuron were detected in only one sample at concentrations lower than the MRLs. The results indicate that the developed LC/MS method is accurate, precise, and sensitive for quantitative and qualitative analysis at low levels of benzoylureas

  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

  7. Ionization of EPA Contaminants in Direct and Dopant-Assisted Atmospheric Pressure Photoionization and Atmospheric Pressure Laser Ionization

    NASA Astrophysics Data System (ADS)

    Kauppila, Tiina J.; Kersten, Hendrik; Benter, Thorsten

    2015-06-01

    Seventy-seven EPA priority environmental pollutants were analyzed using gas chromatography-mass spectrometry (GC-MS) equipped with an optimized atmospheric pressure photoionization (APPI) and an atmospheric pressure laser ionization (APLI) interface with and without dopants. The analyzed compounds included e.g., polycyclic aromatic hydrocarbons (PAHs), nitro compounds, halogenated compounds, aromatic compounds with phenolic, acidic, alcohol, and amino groups, phthalate and adipatic esters, and aliphatic ethers. Toluene, anisole, chlorobenzene, and acetone were tested as dopants. The widest range of analytes was ionized using direct APPI (66/77 compounds). The introduction of dopants decreased the amount of compounds ionized in APPI (e.g., 54/77 with toluene), but in many cases the ionization efficiency increased. While in direct APPI the formation of molecular ions via photoionization was the main ionization reaction, dopant-assisted (DA) APPI promoted ionization reactions, such as charge exchange and proton transfer. Direct APLI ionized a much smaller amount of compounds than APPI (41/77 compounds), showing selectivity towards compounds with low ionization energies (IEs) and long-lived resonantly excited intermediate states. DA-APLI, however, was able to ionize a higher amount of compounds (e.g. 51/77 with toluene), as the ionization took place entirely through dopant-assisted ion/molecule reactions similar to those in DA-APPI. Best ionization efficiency in APPI and APLI (both direct and DA) was obtained for PAHs and aromatics with O- and N-functionalities, whereas nitro compounds and aliphatic ethers were the most difficult to ionize. Halogenated aromatics and esters were (mainly) ionized in APPI, but not in APLI.

  8. Transmission Geometry Laserspray Ionization Vacuum Using an Atmospheric Pressure Inlet

    PubMed Central

    2015-01-01

    This represents the first report of laserspray ionization vacuum (LSIV) with operation directly from atmospheric pressure for use in mass spectrometry. Two different types of electrospray ionization source inlets were converted to LSIV sources by equipping the entrance of the atmospheric pressure inlet aperture with a customized cone that is sealed with a removable glass plate holding the matrix/analyte sample. A laser aligned in transmission geometry (at 180° relative to the inlet) ablates the matrix/analyte sample deposited on the vacuum side of the glass slide. Laser ablation from vacuum requires lower inlet temperature relative to laser ablation at atmospheric pressure. However, higher inlet temperature is required for high-mass analytes, for example, α-chymotrypsinogen (25.6 kDa). Labile compounds such as gangliosides and cardiolipins are detected in the negative ion mode directly from mouse brain tissue as intact doubly deprotonated ions. Multiple charging enhances the ion mobility spectrometry separation of ions derived from complex tissue samples. PMID:24896880

  9. 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 А; 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

  10. 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

  11. Development of an Atmospheric Pressure Ionization Mass Spectrometer

    NASA Technical Reports Server (NTRS)

    1998-01-01

    A commercial atmospheric pressure ionization mass spectrometer (APIMS) was purchased from EXTREL Mass Spectrometry, Inc. (Pittsburgh, PA). Our research objectives were to adapt this instrument and develop techniques for real-time determinations of the concentrations of trace species in the atmosphere. The prototype instrument is capable of making high frequency measurements with no sample preconcentrations. Isotopically labeled standards are used as an internal standard to obtain high precision and to compensate for changes in instrument sensitivity and analyte losses in the sampling manifold as described by Bandy and coworkers. The prototype instrument is capable of being deployed on NASA C130, Electra, P3, and DC8 aircraft. After purchasing and taking delivery by June 1994, we assembled the mass spectrometer, data acquisition, and manifold flow control instrumentation in electronic racks and performed tests.

  12. Diclofenac in municipal wastewater treatment plant: quantification using laser diode thermal desorption--atmospheric pressure chemical ionization--tandem mass spectrometry approach in comparison with an established liquid chromatography-electrospray ionization-tandem mass spectrometry method.

    PubMed

    Lonappan, Linson; Pulicharla, Rama; Rouissi, Tarek; Brar, Satinder K; Verma, Mausam; Surampalli, Rao Y; Valero, José R

    2016-02-12

    Diclofenac (DCF), a prevalent non-steroidal anti-inflammatory drug (NSAID) is often detected in wastewater and surface water. Analysis of the pharmaceuticals in complex matrices is often laden with challenges. In this study a reliable, rapid and sensitive method based on laser diode thermal desorption/atmospheric pressure chemical ionization (LDTD/APCI) coupled with tandem mass spectrometry (MS/MS) has been developed for the quantification of DCF in wastewater and wastewater sludge. An established conventional LC-ESI-MS/MS (liquid chromatography-electrospray ionization-tandem mass spectrometry) method was compared with LDTD-APCI-MS/MS approach. The newly developed LDTD-APCI-MS/MS method reduced the analysis time to 12s in lieu of 12 min for LC-ESI-MS/MS method. The method detection limits for LDTD-APCI-MS/MS method were found to be 270 ng L(-1) (LOD) and 1000 ng L(-1) (LOQ). Furthermore, two extraction procedures, ultrasonic assisted extraction (USE) and accelerated solvent extraction (ASE) for the extraction of DCF from wastewater sludge were compared and ASE with 95.6 ± 7% recovery was effective over USE with 86 ± 4% recovery. The fate and partitioning of DCF in wastewater (WW) and wastewater sludge (WWS) in wastewater treatment plant was also monitored at various stages of treatment in Quebec Urban community wastewater treatment plant. DCF exhibited affinity towards WW than WWS with a presence about 60% of DCF in WW in contrary with theoretical prediction (LogKow=4.51). PMID:26805597

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

    PubMed

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

    2015-07-01

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

  14. Characterization of HOCl using atmospheric pressure ionization mass spectrometry

    SciTech Connect

    Caldwell, T.E.; Foster, K.L.; Benter, T.; Langer, S.; Hemminger, J.C.; Finlayson-Pitts, B.J.

    1999-10-14

    HOCl is an important intermediate in stratospheric and tropospheric chemistry. Although it can be readily measured in laboratory systems at low pressures ({le}20 Torr) using conventional electron impact ionization mass spectrometry, there is a need for a measurement technique that can operate at higher pressures, up to 1 atm in air. One such technique seeing increasing use is atmospheric pressure ionization mass spectrometry (API-MS). The authors report here studies of the API-MS of {approximately}0.5--50 ppm HOCl at a total pressure of 1 atm and room temperature. Major peaks from the ion-adducts with Cl{sup {minus}} and OCI{sup {minus}} were observed. The Br{sup {minus}} adduct of HOCl can also be generated using bromoform in the discharge region of the ion source. At the lower range of HOCl concentrations studied in air, the O{sub 2}{sup {minus}} adduct and small parent peaks assigned to HOCl{sup {minus}} were observed. The species present as minor impurities in the HOCl source (Cl{sub 2}, Cl{sub 2}O and HCl) can be readily distinguished through identification of the parent ion for Cl{sub 2}, or as their adducts with Cl{sup {minus}} and Br{sup {minus}} for Cl{sub 2}O and HCI. The identification of HOCl was confirmed using electron impact ionization time-of-flight mass spectrometry (El-MS). HOCl was quantified using EI-MS to measure the Cl{sub 2} generated when the HOCl reacted heterogeneously on a water-ice/HCl surface and independently by photolysis of the HOCl to generate atomic chlorine, which was trapped using propene and measured as chloroacetone. The implications for the use of API-MS for measuring HOCl in laboratory systems and in ambient air are discussed.

  15. Technical note: Detection of dimethylamine in the low pptv range using nitrate Chemical Ionization-Atmospheric Pressure interface-Time Of Flight (CI-APi-TOF) mass spectrometry

    NASA Astrophysics Data System (ADS)

    Simon, M.; Heinritzi, M.; Herzog, S.; Leiminger, M.; Bianchi, F.; Praplan, A.; Dommen, J.; Curtius, J.; Kürten, A.

    2015-12-01

    Amines are potentially important for atmospheric new particle formation and therefore the demand for highly sensitive gas phase amine measurements has emerged in the last several years. Nitrate Chemical Ionization Mass Spectrometry (CIMS) is routinely used for the measurement of gas phase-sulfuric acid in the sub-pptv range. Furthermore, Extremely Low Volatile Organic Compounds (ELVOCs) can be detected with a nitrate CIMS. In this study we demonstrate that a nitrate CIMS can also be used for the sensitive measurement of dimethylamine ((CH3)2NH, DMA) using the NO3-(HNO3)1-2(DMA) cluster ion signals. This observation was made at the CLOUD aerosol chamber, which was also used for calibration measurements. Good linearity between 0 and ~120 pptv of DMA as well as a sub-pptv detection limit of 0.7 pptv for a 10 min integration time are demonstrated at 278 K and 38 % RH.

  16. Sequential solid phase extraction protocol followed by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry for the trace determination of non ionic polyethoxylated surfactants in tannery wastewaters

    SciTech Connect

    Castillo, M.; Barcelo, D.; Ventura, F.

    1999-06-01

    Automated solid-phase extraction (SPE) with C18 and styrene-divinylbenzene cartridges in series was used for the preconcentration of non ionic polyethoxylated surfactants in tannery wastewater. Fractionated extracts were analyzed by LC-MS using Atmospheric Pressure Chemical Ionization (APCI) in the Positive and Negative Ion modes. Recoveries for nonionic surfactants were approximately of 72, 90 and 80% for polyethylene glycols, nonylphenol and alcohol ethoxylates in the polar, aromatic and medium polarity fractions, respectively. Data acquisition in the selected ion monitoring mode afforded limits of quantification from 0.1 to 0.8 {micro}g/l for tridecylic polyethoxylated alcohol and polyethoxylated glycol, respectively, in the complex tannery wastewaters. The tannery effluents investigated contained between 0.03 to 3.0 mg/l of polyethylene glycol and nonylphenol polyethoxylate, respectively.

  17. 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

  18. 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.

  19. Plasma Ion Sources for Atmospheric Pressure Ionization Mass Spectrometry.

    NASA Astrophysics Data System (ADS)

    Zhao, Jian-Guo

    1994-01-01

    Atmospheric pressure ionization (API) sources using direct-current (DC) and radio-frequency (RF) plasma have been developed in this thesis work. These ion sources can provide stable discharge currents of ~ 1 mA, 2-3 orders of magnitude larger than that of the corona discharge, a widely used API source. The plasmas can be generated and maintained in 1 atm of various buffer gases by applying -500 to -1000 V (DC plasma) or 1-15 W with a frequency of 165 kHz (RF plasma) on the needle electrode. These ion sources have been used with liquid injection to detect various organic compounds of pharmaceutical, biotechnological and environmental interest. Key features of these ion sources include soft ionization with the protonated molecule as the largest peak, and superb sensitivity with detection limits in the low picogram or femtomole range and a linear dynamic range over ~4 orders of magnitude. The RF plasma has advantages over the DC plasma in its ability to operate in various buffer gases and to produce a more stable plasma. Factors influencing the performance of the ion sources have been studied, including RF power level, liquid flow rate, chamber temperature, solvent composition, and voltage affecting the collision induced dissociation (CID). Ionization of hydrocarbons by the RF plasma API source was also studied. Soft ionization is generally produced. To obtain high sensitivity, the ion source must be very dry and the needle-to-orifice distance must be small. Nitric oxide was used to enhance the sensitivity. The RF plasma source was then used for the analysis of hydrocarbons in auto emissions. Comparisons between the corona discharge and the RF plasma have been made in terms of discharge current, ion residence time, and the ion source model. The RF plasma source provides larger linear dynamic range and higher sensitivity than the corona discharge, due to its much larger discharge current. The RF plasma was also observed to provide longer ion residence times and was not

  20. Detection of dimethylamine in the low pptv range using nitrate chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry

    NASA Astrophysics Data System (ADS)

    Simon, Mario; Heinritzi, Martin; Herzog, Stephan; Leiminger, Markus; Bianchi, Federico; Praplan, Arnaud; Dommen, Josef; Curtius, Joachim; Kürten, Andreas

    2016-05-01

    Amines are potentially important for atmospheric new particle formation, but their concentrations are usually low with typical mixing ratios in the pptv range or even smaller. Therefore, the demand for highly sensitive gas-phase amine measurements has emerged in the last several years. Nitrate chemical ionization mass spectrometry (CIMS) is routinely used for the measurement of gas-phase sulfuric acid in the sub-pptv range. Furthermore, extremely low volatile organic compounds (ELVOCs) can be detected with a nitrate CIMS. In this study we demonstrate that a nitrate CIMS can also be used for the sensitive measurement of dimethylamine (DMA, (CH3)2NH) using the NO3-•(HNO3)1 - 2• (DMA) cluster ion signal. Calibration measurements were made at the CLOUD chamber during two different measurement campaigns. Good linearity between 0 and ˜ 120 pptv of DMA as well as a sub-pptv detection limit of 0.7 pptv for a 10 min integration time are demonstrated at 278 K and 38 % RH.

  1. 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

  2. Novel analytical approach for brominated flame retardants based on the use of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry with emphasis in highly brominated congeners.

    PubMed

    Portolés, Tania; Sales, Carlos; Gómara, Belén; Sancho, Juan Vicente; Beltrán, Joaquim; Herrero, Laura; González, María José; Hernández, Félix

    2015-10-01

    The analysis of brominated flame retardants (BFRs) commonly relies on the use of gas chromatography coupled to mass spectrometry (GC-MS) operating in electron ionization (EI) and electron capture negative ionization (ECNI) modes using quadrupole, triple quadrupole, ion trap, and magnetic sector analyzers. However, these brominated contaminants are examples of compounds for which a soft and robust ionization technique might be favorable since they show high fragmentation in EI and low specificity in ECNI. In addition, the low limits of quantification (0.01 ng/g) required by European Commission Recommendation 2014/118/EU on the monitoring of traces of BFRs in food put stress on the use of highly sensitive techniques/methods. In this work, a new approach for the extremely sensitive determination of BFRs taking profit of the potential of atmospheric pressure chemical ionization (APCI) combined with GC and triple quadrupole (QqQ) mass analyzer is proposed. The objective was to explore the potential of this approach for the BFRs determination in samples at pg/g levels, taking marine samples and a cream sample as a model. Ionization and fragmentation behavior of 14 PBDEs (congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two novel BFRs, decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), in the GC-APCI-MS system has been investigated. The formation of highly abundant (quasi) molecular ion was the main advantage observed in relation to EI. Thus, a notable improvement in sensitivity and specificity was observed when using it as precursor ion in tandem MS. The improved detectability (LODs < 10 fg) achieved when using APCI compared to EI has been demonstrated, which is especially relevant for highly brominated congeners. Analysis of samples from an intercomparison exercise and samples from the marine field showed the potential of this approach for the reliable identification and quantification at very low

  3. Real-time flavor analysis: optimization of a proton-transfer-mass spectrometer and comparison with an atmospheric pressure chemical ionization mass spectrometer with an MS-nose interface.

    PubMed

    Avison, Shane J

    2013-03-01

    Two techniques are recognized for the real-time analysis of flavors during eating and drinking, atmospheric pressure chemical ionization mass spectrometry (APCI-MS), and proton transfer reaction mass spectrometry (PTR-MS). APCI-MS was developed for the analysis of flavors and fragrances, whereas PTR-MS was originally developed and optimized for the analysis of atmospheric pollutants. Here, the suitability of the two techniques for real-time flavor analysis is compared, using a varied range of common flavor compounds. An Ionicon PTR-MS was first optimized and then its performance critically compared with that of APCI-MS. Performance was gauged using the capacity for soft ionization, dynamic linear range, and limit of detection. Optimization of the PTR-MS increased the average sensitivity by a factor of more than 3. However, even with this increase in sensitivity, the Limit of Detection was typically 10 times higher and the Dynamic Linear Range ten times narrower than that of the APCI-MS. PMID:23394597

  4. 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 3β-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

  5. Analysis of secondary organic aerosol using a Micro-Orifice Volatilization Impactor (MOVI) coupled to an ion trap mass spectrometer with atmospheric pressure chemical ionization (APCI-IT/MS)

    NASA Astrophysics Data System (ADS)

    Brueggemann, M.; Vogel, A.; Hoffmann, T.

    2012-04-01

    We describe the development and characterization of a Micro-Orifice Volatilization Impactor (MOVI) which is coupled to an ion trap mass spectrometer with atmospheric pressure chemical ionization (APCI-IT/MS), and its application in laboratory and field measurements. The MOVI-APCI-IT/MS allows the quantification of organic acids and other oxidation products of volatile organic compounds (VOCs) in secondary organic aerosols (SOA) on a semi-continuous basis. Furthermore, the vapor pressure and saturation concentration of the particle components can be estimated. The MOVI was first described in 2010 by Yatavelli and Thornton (Yatavelli and Thornton, 2010). It is a single stage, multi-nozzle impactor with 100 nozzles, each having a diameter of 150 μm. At a flow-rate of 10 L·min-1 air is drawn through the MOVI and particles are collected on a deposition plate. The cut-point diameter (d50, diameter of 50% collection efficiency) is at 130 nm. A low pressure-drop of only 5.3% of atmospheric pressure behind the nozzles allows collecting not only low-volatile but even semi-volatile compounds, which are an important part of SOA. After collecting particles hydrocarbon-free synthetic air is led over the collection surface into the APCI-IT/MS and the collection surface is heated up to 120 ° C in less than 200 s, volatilizing the sampled SOA. The vaporized compounds are transferred into the ion source and subsequently analyzed by mass spectrometry. Due to the soft ionization at atmospheric pressure the obtained mass spectra show only low fragmentations and can easily be interpreted. In laboratory experiments the MOVI-APCI-IT/MS was used for the chemical analysis of SOA generated from α-pinene-ozonolysis in a smog chamber. The limit of detection was found at 7.3 ng for pinic acid. The vapor pressure log p0 and the saturation concentration C25* for pinic acid were calculated from the desorption temperature using the method presented by Faulhaber et al. (Faulhaber et al., 2009

  6. Profiling of acylcarnitines and sterols from dried blood or plasma spot by atmospheric pressure thermal desorption chemical ionization (APTDCI) tandem mass spectrometry.

    PubMed

    Corso, Gaetano; D'Apolito, Oceania; Garofalo, Daniela; Paglia, Giuseppe; Dello Russo, Antonio

    2011-11-01

    Free carnitine and acylcarnitines play an important role in the metabolism of fatty acids. Sterols are structural lipids found in the membranes of many eukaryotic cells, and they also have functional roles such as the regulation of membrane permeability and fluidity, activity of membrane-bound enzymes and signals transduction. Abnormal profiles of these compounds in biological fluids may be useful markers of metabolic changes. In this review, we describe the subset of the lipidome represented by acylcarnitines and sterols, and we summarize how these compounds have been analyzed in the past. Over the last 50years, lipid mass spectrometry (MS) has evolved to become one of the most useful techniques for metabolic analysis. Today, the introduction of new ambient ionization techniques coupled to MS (AMS), which are characterized by the direct desorbing/ionizing of molecules from solid samples, is generating new possibilities for in situ analysis. Recently, we developed an AMS approach called APTDCI to desorb/ionize using a heated gas flow and an electrical discharge to directly analyze sterols and indirectly investigate acylcarnitines in dried blood or plasma spot samples. Here, we also describe the APTDCI method and some of its clinical applications, and we underline the common complications and issues that remain to be resolved. PMID:21683155

  7. 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

  8. Atmospheric pressure ionization LC-MS-MS determination of urushiol congeners.

    PubMed

    Draper, William M; Wijekoon, Donald; McKinney, Michael; Behniwal, Paramjit; Perera, S Kusum; Flessel, C Peter

    2002-03-27

    This paper describes atmospheric pressure ionization (API) LC-MS-MS determination of urushiols, 3-n-alkenyl- and -alkyl-substituted catechols responsible for poison oak dermatitis. Urushiol was isolated from Western poison oak according to the method of Elsohly et al. (1) (J. Nat. Prod. 1982, 45, 532-538)-the purified preparation contained C(17)- and C(15)-substituted urushiols with zero, one, two, and three double bonds as determined from GC-MS analysis of trimethylsilyl derivatives. Urushiol mixtures were separated on a C(18) reversed phase HPLC column with a methanol-water gradient with urushiols eluting in 100% methanol. Atmospheric pressure chemical ionization (APCI) produced primarily [M - H](-) and MH(+) molecule ions. Electrospray ionization (ESI) yielded [M - H](-) and adduct ions including [M + Cl](-). Daughter ions of [M - H](-) included quinoid radical anions ([M - H - H(2)](-) and m/z 122(-)) and a benzofuran phenate (m/z 135(-)). A suite of hydrocarbon fragments were produced by collision-induced dissociation of MH(+) directly or via an intermediate [MH - H(2)O](+) daughter ion. Six urushiol congeners, one not previously reported in poison oak, were determined by negative ion API-LC-MS-MS with detection limits of approximately 8 pg/microL (ESI) and approximately 800 pg/microL (APCI). API-LC-MS-MS was used to determine urushiol in surface wipes, air samples, and plant materials. PMID:11902923

  9. Evaluation of the capabilities of atmospheric pressure chemical ionization source coupled to tandem mass spectrometry for the determination of dioxin-like polychlorobiphenyls in complex-matrix food samples.

    PubMed

    Portolés, T; Sales, C; Abalos, M; Sauló, J; Abad, E

    2016-09-21

    The use of the novel atmospheric pressure chemical ionization (APCI) source for gas chromatography (GC) coupled to triple quadrupole using tandem mass spectrometry (MS/MS) and its potential for the simultaneous determination of the 12 dioxin-like polychlorobiphenyls (DL-PCBs) in complex food and feed matrices has been evaluated. In first place, ionization and fragmentation behavior of DL-PCBs on the APCI source under charge transfer conditions has been studied followed by their fragmentation in the collision cell. Linearity, repeatability and sensitivity have been studied obtaining instrumental limits of detection and quantification of 0.0025 and 0.005 pg μL(-1) (2.5 and 5 fg on column) respectively for every DL-PCB. Finally, application to real samples has been carried out and DL-PCB congeners (PCB 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) have been detected in the different samples in the range of 0.40-10000 pg g(-1). GC-(APCI)MS/MS has been proved as a suitable alternative to the traditionally accepted confirmation method based on the use of high resolution mass spectrometry and other triple quadrupole tandem mass spectrometry techniques operating with electron ionization. The development of MS/MS methodologies for the analysis of dioxins and DL-PCBs is nowadays particularly important, since this technique was included as a confirmatory method in the present European Union regulations that establish the requirements for the determination of these compounds in food and feed matrices. PMID:27590550

  10. Determination of organophosphate flame retardants and plasticizers in lipid-rich matrices using dispersive solid-phase extraction as a sample cleanup step and ultra-high performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Chu, Shaogang; Letcher, Robert J

    2015-07-23

    A fast, robust and highly sensitive analysis method for determination of trace levels of organophosphate ester (OPE) flame retardants and plasticizers in lipid-rich samples was presently developed, and based on ultra-high performance liquid chromatography-tandem mass spectrometry coupled to a positive atmospheric pressure chemical ionization source (UHPLC-MS/MS-APCI(+)). The target OPEs in the sample were extracted from the biota samples, such as egg and liver, by ultrasonic extraction, and cleaned up further by dispersive solid phase extraction (d-ESP). As a result, background contamination was largely reduced. Different dispersive ESP sorbents were tested and primary secondary amine (PSA) bonded silica sorbents showed the best recoveries for these target OPEs. The recoveries obtained were in the range 54-113% (RSD<17%), with method limits of quantification (MLOQs) ranging between 0.06 and 0.29ng/g in egg, and 0.05 and 0.50ng/g w.w. in liver sample. The matrix effects (MEs) associated with using APCI(+) and ESI(+) sources were investigated. APCI(+) showed much less ion suppression than ESI(+) for the determination of these OPEs. For egg and liver samples, the APCI(+) ME values ranged from 40% to 94%, while ESI(+) ME values ranged from 0% to 36%. Although APCI(+) was used for the determination of OPEs, the ionization mechanism might mainly be a thermospray ionization process. This UHPLC-MS/MS-APCI(+) method showed good response linearity for calibration (R2>0.99). The proposed method was applied to real environmental bird egg and fish samples, where several OPE were quantifiable and different OPE patterns was observed between samples. PMID:26231904

  11. Method development for the determination of 24S-hydroxycholesterol in human plasma without derivatization by high-performance liquid chromatography with tandem mass spectrometry in atmospheric pressure chemical ionization mode.

    PubMed

    Sugimoto, Hiroshi; Kakehi, Masaaki; Satomi, Yoshinori; Kamiguchi, Hidenori; Jinno, Fumihiro

    2015-10-01

    We developed a highly sensitive and specific high-performance liquid chromatography with tandem mass spectrometry method with an atmospheric pressure chemical ionization interface to determine 24S-hydroxycholesterol, a major metabolite of cholesterol formed by cytochrome P450 family 46A1, in human plasma without any derivatization step. Phosphate buffered saline including 1% Tween 80 was used as the surrogate matrix for preparation of calibration curves and quality control samples. The saponification process to convert esterified 24S-hydroxycholesterol to free sterols was optimized, followed by liquid-liquid extraction using hexane. Chromatographic separation of 24S-hydroxycholesterol from other isobaric endogenous oxysterols was successfully achieved with gradient mobile phase comprised of 0.1% propionic acid and acetonitrile using L-column2 ODS (2 μm, 2.1 mm id × 150 mm). This assay was capable of determining 24S-hydroxycholesterol in human plasma (200 μL) ranging from 1 to 100 ng/mL with acceptable intra- and inter-day precision and accuracy. The potential risk of in vitro formation of 24S-hydroxycholesterol by oxidation from endogenous cholesterol in human plasma was found to be negligible. The stability of 24S-hydroxycholesterol in relevant solvents and human plasma was confirmed. This method was successfully applied to quantify the plasma concentrations of 24S-hydroxycholesterol in male and female volunteers. PMID:26249017

  12. Identification of organic hydroperoxides and hydroperoxy acids in secondary organic aerosol formed during the ozonolysis of different monoterpenes and sesquiterpenes by on-line analysis using atmospheric pressure chemical ionization ion trap mass spectrometry.

    PubMed

    Reinnig, Marc-Christopher; Warnke, Jörg; Hoffmann, Thorsten

    2009-06-01

    On-line ion trap mass spectrometry (ITMS) enables the real-time characterization of reaction products of secondary organic aerosol (SOA). The analysis was conducted by directly introducing the aerosol particles into the ion source. Positive-ion chemical ionization at atmospheric pressure (APCI(+)) ITMS was used for the characterization of constituents of biogenic SOA produced in reaction-chamber experiments. APCI in the positive-ion mode usually enables the detection of [M+H](+) ions of the individual SOA components. In this paper the identification of organic peroxides from biogenic volatile organic compounds (VOCs) by on-line APCI-ITMS is presented. Organic peroxides containing a hydroperoxy group, generated by gas-phase ozonolysis of monoterpenes (alpha-pinene and beta-pinene) and sesquiterpenes (alpha-cedrene and alpha-copaene), could be detected via on-line APCI(+)-MS/MS experiments. A characteristic neutral loss of 34 Da (hydrogen peroxide, H(2)O(2)) in the on-line MS/MS spectra is a clear indication for the existence of an organic peroxide, containing a hydroperoxy functional group. PMID:19412924

  13. Quality classification of Spanish olive oils by untargeted gas chromatography coupled to hybrid quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization and metabolomics-based statistical approach.

    PubMed

    Sales, C; Cervera, M I; Gil, R; Portolés, T; Pitarch, E; Beltran, J

    2017-02-01

    The novel atmospheric pressure chemical ionization (APCI) source has been used in combination with gas chromatography (GC) coupled to hybrid quadrupole time-of-flight (QTOF) mass spectrometry (MS) for determination of volatile components of olive oil, enhancing its potential for classification of olive oil samples according to their quality using a metabolomics-based approach. The full-spectrum acquisition has allowed the detection of volatile organic compounds (VOCs) in olive oil samples, including Extra Virgin, Virgin and Lampante qualities. A dynamic headspace extraction with cartridge solvent elution was applied. The metabolomics strategy consisted of three different steps: a full mass spectral alignment of GC-MS data using MzMine 2.0, a multivariate analysis using Ez-Info and the creation of the statistical model with combinations of responses for molecular fragments. The model was finally validated using blind samples, obtaining an accuracy in oil classification of 70%, taking the official established method, "PANEL TEST", as reference. PMID:27596432

  14. Comparative study of the flavonoids of some Verbena species cultivated in Egypt by using high-performance liquid chromatography coupled with ultraviolet spectroscopy and atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    El-Hela, Atef A; Al-Amier, Hussein A; Ibrahim, Taghreed A

    2010-10-01

    Verbena rigida L., Verbena tenera Spreng. and Verbena venosa L. were investigated for their flavonoid content. Analysis was carried out by high-performance liquid chromatography coupled to diode array UV detection (LC-UV), using different techniques, also using post-column addition of shift reagents, afforded precise structural information about the position of the free hydroxyl groups in the flavonoid nucleus. LC-MS using atmospheric pressure chemical ionization (APCI) in the positive mode provided the molecular weight, the number of hydroxyl groups, the number of sugars and an idea about the substitution pattern of the flavonoid. On-line UV and MS data demonstrated the presence of orientin, vitexin, isovitexin, luteolin, luteolin 7-O-glucoside, apigenin 7-O-glucoside in addition to luteolin, chryseriol and apigenin aglycones in the three Verbena species with different concentrations. Quantitative determination of flavonoid content revealed the presence of 69.84 mg/g dry sample, 88.26 mg/g dry sample and 85.82 mg/g dry sample total flavonoid compounds in V. rigida L., V. tenera Spreng. and V. venosa L., respectively. The method developed for identification is useful for further chromatographic fingerprinting of plant flavonoids. PMID:20817165

  15. Dispersive liquid-liquid microextraction for the determination of macrocyclic lactones in milk by liquid chromatography with diode array detection and atmospheric pressure chemical ionization ion-trap tandem mass spectrometry.

    PubMed

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

    2013-03-22

    Eprinomectin (EPRI), abamectin (ABA), doramectin (DOR), moxidectin (MOX) and ivermectin (IVM) were determined in milk samples using dispersive liquid-liquid microextraction (DLLME) and liquid chromatography with diode array detection (LC-DAD) coupled to atmospheric pressure chemical ionization in negative ion mode ion-trap tandem mass spectrometry (APCI-IT-MS/MS). Milk proteins were removed by precipitation with trichloroacetic acid and the analytes were preconcentrated using 2mL of acetonitrile containing 200μL of chloroform as extraction mixture. The effect of several parameters for the liquid-liquid microextraction efficiency was evaluated. Standard additions method was used for quantification purposes, the correlation coefficients were better than 0.9970 in all cases and the quantification limits ranged from 1.0 to 4.7ngg(-1) and from 0.1 to 2.4ngg(-1) when using DAD and MS, respectively. The DLLME-LC-APCI-IT-MS/MS optimized method was successfully applied to different milk samples and none of the studied analytes was detected in the samples studied. The recoveries for milk samples spiked at concentration levels ranging between 0.5 and 50ngg(-1), depending on the compound, were between 89.5 and 105%, with relative standard deviations lower than 9% (n=135). Simplicity, rapidity and reliability are important advantages of the proposed method, while the sample preparation step can be regarded as environmentally friendly. PMID:23415139

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

    PubMed

    Marotta, Ester; Paradisi, Cristina; Scorrano, Gianfranco

    2004-07-01

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

  17. High-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry and gas chromatography-flame ionization detection characterization of Delta5-polyenoic fatty acids in triacylglycerols from conifer seed oils.

    PubMed

    Lísa, Miroslav; Holcapek, Michal; Rezanka, Tomás; Kabátová, Nadezda

    2007-03-30

    Edible conifer seeds can serve as a source of triacylglycerols (TGs) with unusual Delta5 unsaturated polymethylene interrupted fatty acids (UPIFAs), such as cis-5,9-octadecadienoic (taxoleic), cis-5,9,12-octadecatrienoic (pinolenic), cis-5,11-eicosadienoic (keteleeronic) and cis-5,11,14-eicosatrienoic acids (sciadonic). Conifer seed oils from European Larch (Larix decidua), Norway Spruce (Picea abies) and European Silver Fir (Abies alba) have been analyzed by non-aqueous reversed-phase high-performance liquid chromatography (NARP-HPLC) with atmospheric pressure chemical ionisation (APCI)-MS detection. The influence of different positions of double bonds in Delta5-UPIFAs on the retention and fragmentation behavior is described and used for the successful identification of TGs in each oil. TGs containing Delta5-UPIFAs have a higher retention in comparison with common TGs found in plant oils with single methylene interrupted Delta6(9)-FAs and also significantly changed relative abundances of fragment ions in APCI mass spectra. Results obtained from HPLC/MS analyses are supported by validated GC/FID analyses of fatty acid methyl esters after the transesterification. The total content of Delta5-UPIFAs is about 32% for European Larch, 27% for Norway Spruce and 20% for European Silver Fir. In total, 20 FAs with acyl chain lengths from 16 to 24 carbon atoms and from 0 to 3 double bonds have been identified in 64 triacylglycerols from 3 conifer seed oils. PMID:17307191

  18. A rapid and simple method for the simultaneous determination of four endogenous monoamine neurotransmitters in rat brain using hydrophilic interaction liquid chromatography coupled with atmospheric-pressure chemical ionization tandem mass spectrometry.

    PubMed

    Zhou, Wenbin; Zhu, Bangjie; Liu, Feng; Lyu, Chunming; Zhang, Shen; Yan, Chao; Cheng, Yu; Wei, Hai

    2015-10-01

    Endogenous monoamine neurotransmitters play an essential role in neural communication in mammalians. Many quantitative methods for endogenous monoamines have been developed during recent decades. Yet, matrix effect was usually a challenge in the quantification, in many cases asking for tedious sample preparation or sacrificing sensitivity. In this work, a simple, fast and sensitive method with no matrix effect was developed to simultaneously determine four endogenous monoamines including serotonin, dopamine, epinephrine and norepinephrine in rat brain tissues, using hydrophilic interaction liquid chromatography coupled with atmospheric-pressure chemical ionization tandem mass spectrometry. Various conditions, including columns, chromatographic conditions, ion source, MS/MS conditions, and brain tissue preparation methods, were optimized and validated. Pre-weighed 20mg brain sample could be effectively and reproducibly homogenized and protein-precipitated by 20 times value of 0.2% formic acid in cold organic solvents (methanol-acetonitrile, 10:90, v/v). This method exhibited excellent linearity for all analytes (regression coefficients>0.998 or 0.999). The precision, expressed as coefficients of variation, was less than 3.43% for intra-day analyses and ranged from 4.17% to 15.5% for inter-day analyses. Good performance was showed in limit of detection (between 0.3nM and 3.0nM for all analytes), recovery (90.8-120%), matrix effect (84.4-107%), accuracy (89.8-100%) and stability (88.3-104%). The validated method was well applied to simultaneously determine the endogenous serotonin, dopamine, epinephrine and norepinephrine in four brain sections of 18 Wistar rats. The quantification of four endogenous monoamines in rat brain performed excellently in the sensitivity, high throughput, simple sample preparation and matrix effect. PMID:26363373

  19. 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

  20. An approach based on ultrahigh performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry allowing the quantification of both individual phytosteryl and phytostanyl fatty acid esters in complex mixtures.

    PubMed

    Scholz, Birgit; Menzel, Nicole; Lander, Vera; Engel, Karl-Heinz

    2016-01-15

    A method for the analysis of both individual phytosteryl and phytostanyl fatty acid esters in complex mixtures was established. The approach was based on a previously not described combination of three elements: (i) the formation of [M-FA+H](+) fragment ions via APCI (atmospheric pressure chemical ionization), (ii) a highly efficient UHPLC-based separation on a 1.7 μ C8 column, previously established for phytostanyl fatty acid esters, allowing the distinction of individual fatty acid esters sharing the same sterol/stanol nucleus and of isotope peaks of phytosteryl fatty acid esters and corresponding phytostanyl fatty acid esters based on these [M-FA+H](+) fragment ions, and (iii) the adjustment of the APCI conditions allowing the differential APCI-MS-SIM (single ion monitoring) detection of phytostanyl esters of linoleic and linolenic acid based on their distinct formation of a [M+H](+) ion. The usefulness of the methodology was demonstrated by the analysis of a commercially available enriched margarine. Two runs per sample allowed the quantification of 35 target analytes; the total amounts of esters were between 124.7 and 125.3g/kg, being in good agreement with the labelled 125 g/kg. Validation data were elaborated for 35 individual fatty acid esters of sitosterol, campesterol, brassicasterol, stigmasterol, sitostanol and campestanol. Recovery rates ranged from 95 to 106%; the coefficients of variation were consistently <5%, except for stigmasteryl-18:1. The approach describes for the first time a quantification of both individual phytosteryl and phytostanyl fatty acid esters and thus closes an analytical gap related to this class of health-relevant food constituents. PMID:26718186

  1. 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

  2. Development of a new multi-residue laser diode thermal desorption atmospheric pressure chemical ionization tandem mass spectrometry method for the detection and quantification of pesticides and pharmaceuticals in wastewater samples.

    PubMed

    Boisvert, Michel; Fayad, Paul B; Sauvé, Sébastien

    2012-11-19

    A new solid phase extraction (SPE) method coupled to a high throughput sample analysis technique was developed for the simultaneous determination of nine selected emerging contaminants in wastewater (atrazine, desethylatrazine, 17β-estradiol, ethynylestradiol, norethindrone, caffeine, carbamazepine, diclofenac and sulfamethoxazole). We specifically included pharmaceutical compounds from multiple therapeutic classes, as well as pesticides. Sample pre-concentration and clean-up was performed using a mixed-mode SPE cartridge (Strata ABW) having both cation and anion exchange properties, followed by analysis by laser diode thermal desorption atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). The LDTD interface is a new high-throughput sample introduction method, which reduces total analysis time to less than 15s per sample as compared to minutes with traditional liquid-chromatography coupled to tandem mass spectrometry (LC-MS/MS). Several SPE parameters were evaluated in order to optimize recovery efficiencies when extracting analytes from wastewater, such as the nature of the stationary phase, the loading flow rate, the extraction pH, the volume and composition of the washing solution and the initial sample volume. The method was successfully applied to real wastewater samples from the primary sedimentation tank of a municipal wastewater treatment plant. Recoveries of target compounds from wastewater ranged from 78% to 106%, the limit of detection ranged from 30 to 122ng L(-1) while the limit of quantification ranged from 90 to 370ng L(-1). Calibration curves in the wastewater matrix showed good linearity (R(2)≥0.991) for all target analytes and the intraday and interday coefficient of variation was below 15%, reflecting a good precision. PMID:23140957

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

    PubMed

    Martínez, K; Ferrer, I; Barceló, D

    2000-05-19

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

  4. Quantification of β-carotene, retinol, retinyl acetate and retinyl palmitate in enriched fruit juices using dispersive liquid-liquid microextraction coupled to liquid chromatography with fluorescence detection and atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

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

    2013-02-01

    A detailed optimization of dispersive liquid-liquid microextraction (DLLME) was carried out for developing liquid chromatographic (HPLC) techniques, using both fluorescence and atmospheric pressure chemical ionization mass spectrometric (APCI-MS) detection, for the simultaneous analysis of preforms of vitamin A: retinol (R), retinyl acetate (RA), retinyl palmitate (RP) and β-carotene (β-C). The HPLC analyses were carried out using a mobile phase composed of methanol and water, with gradient elution. The APCI-MS and fluorescence spectra permitted the correct identification of compounds in the analyzed samples. Parameters affecting DLLME were optimized using 2 mL of methanol (disperser solvent) containing 150 μL carbon tetrachloride (extraction solvent). The precision ranged from 6% to 8% (RSD) and the limits of detection were between 0.03 and 1.4 ng mL(-1), depending on the compound. The enrichment factor values were in the 21-44 range. Juice samples were analyzed without saponification and no matrix effect was found when using fluorescence detection, so calibration was possible with aqueous standards. However, a matrix effect appeared with APCI-MS, in which case it was necessary to apply matrix-matched calibration. There was great variability in the forms of vitamin A present in the juices, the most abundant ester being retinyl acetate (0.04 to 3.4 μg mL(-1)), followed by the amount of retinol (0.01 to 0.16 μg mL(-1)), while retinyl palmitate was not detected, except in the milk-containing juice, in which RP was the main form. The representative carotenoid β-carotene was present in the orange, peach, mango and multifruit juices in high amounts. The method was validated using two certified reference materials. PMID:23290361

  5. Established and Emerging Atmospheric Pressure Surface Sampling/Ionization Techniques for Mass Spectrometry

    SciTech Connect

    Van Berkel, Gary J; Pasilis, Sofie P; Ovchinnikova, Olga S

    2008-01-01

    The number and type of atmospheric pressure techniques suitable for sampling analytes from surfaces, forming ions from those analytes, and subsequently transporting those ions into vacuum for interrogation by mass spectrometry has rapidly expanded over the last several years. Moreover, the literature in this area is complicated by an explosion in acronyms for these techniques, many of which provide no information relating to the chemical or physical processes involved. In this review, we sort this vast array of techniques into a relatively few categories on the basis of the approaches used for surface sampling and ionization. For each technique, we explain, as best known, many of the underlying principles of operation, describe representative applications, and in some cases, discuss needed research or advancements and attempt to forecast their future analytical utility.

  6. 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

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

    PubMed

    Chen, L C; Ninomiya, S; Hiraoka, K

    2016-06-01

    Pressure is a key parameter for an ionization source. In this Special Feature article, Lee Chuin Chen and colleagues review super-atmospheric pressure ionization MS with electrospray, corona-discharge-based chemical ionization, and field desorption. They routinely run their mass spectrometer with ion source pressures ranging from several to several tens of atmospheres. A number of strategies have been used to preserve the high vacuum of the instrument while working with a high-pressure (HP) ion source. A recent prototype uses a booster pump with variable pumping speed added to the first pumping stage of the mass spectrometer to regulate a constant vacuum pressure. Further, a new HP-ESI source allowing rapid (a few seconds) online protein digestion MS is also reported. Dr. Lee Chuin Chen is Associate Professor in the Department of Interdisciplinary Research at the University of Yamanashi (Yamanashi, Japan). His main research interest is the development of novel mass spectrometric methods for in-situ medical diagnosis. PMID:27270871

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

    PubMed

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

    2016-06-01

    Ion source pressure plays a significant role in the process of ionization and the subsequent ion transmission inside a mass spectrometer. Pressurizing the ion source to a gas pressure greater than atmospheric pressure is a relatively new approach that aims to further improve the performance of atmospheric pressure ionization sources. For example, under a super-atmospheric pressure environment, a stable electrospray can be sustained for liquid with high surface tension such as pure water, because of the suppression of electric discharge. Even for nano-electrospray ionization (nano-ESI), which is known to work with aqueous solution, its stability and sensitivity can also be enhanced, particularly in the negative mode when the ion source is pressurized. A brief review on the development of super-atmospheric pressure ion sources, including high-pressure electrospray, field desorption and superheated ESI, and the strategies to interface these ion sources to a mass spectrometer will be given. Using a recent ESI prototype with an operating temperature at 220 °C under 27 atm, we also demonstrate that it is possible to achieve an online Asp-specific protein digestion analysis in which the whole processes of digestion, ionization and MS acquisition could be completed on the order of a few seconds. This method is fast, and the reaction can even be monitored on a near-real-time basis. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27270863

  9. Supercritical fluid chromatography coupled with in-source atmospheric pressure ionization hydrogen/deuterium exchange mass spectrometry for compound speciation.

    PubMed

    Cho, Yunju; Choi, Man-Ho; Kim, Byungjoo; Kim, Sunghwan

    2016-04-29

    An experimental setup for the speciation of compounds by hydrogen/deuterium exchange (HDX) with atmospheric pressure ionization while performing chromatographic separation is presented. The proposed experimental setup combines the high performance supercritical fluid chromatography (SFC) system that can be readily used as an inlet for mass spectrometry (MS) and atmospheric pressure photo ionization (APPI) or atmospheric pressure chemical ionization (APCI) HDX. This combination overcomes the limitation of an approach using conventional liquid chromatography (LC) by minimizing the amount of deuterium solvents used for separation. In the SFC separation, supercritical CO2 was used as a major component of the mobile phase, and methanol was used as a minor co-solvent. By using deuterated methanol (CH3OD), AP HDX was achieved during SFC separation. To prove the concept, thirty one nitrogen- and/or oxygen-containing standard compounds were analyzed by SFC-AP HDX MS. The compounds were successfully speciated from the obtained SFC-MS spectra. The exchange ions were observed with as low as 1% of CH3OD in the mobile phase, and separation could be performed within approximately 20min using approximately 0.24 mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method. PMID:27020885

  10. Measurement of the First Townsend's Ionization Coefficients in Helium, Air, and Nitrogen at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Ran, Junxia; Luo, Haiyun; Yue, Yang; Wang, Xinxin

    2014-07-01

    In the past the first Townsend’s ionization coefficient α could only be measured with Townsend discharge in gases at low pressure. After realizing Townsend discharge in some gases at atmospheric pressure by using dielectric barrier electrodes, we had developed a new method for measuring α coefficient at atmospheric pressure, a new optical method based on the discharge images taken with ICCD camera. With this newly developed method α coefficient in helium, nitrogen and air at atmospheric pressure were measured. The results were found to be in good agreement with the data obtained at lower pressure but same reduced field E/p by other groups. It seems that the value of α coefficient is sensitive to the purity of the working gas.

  11. Atmospheric Pressure Surface Sampling/Ionization Techniques for Direct Coupling of Planar Separations with Mass Spectrometry

    SciTech Connect

    Pasilis, Sofie P; Van Berkel, Gary J

    2010-01-01

    Planar separations, which include thin layer chromatography and gel electrophoresis, are in widespread use as important and powerful tools for conducting separations of complex mixtures. To increase the utility of planar separations, new methods are needed that allow in-situ characterization of the individual components of the separated mixtures. A large number of atmospheric pressure surface sampling and ionization techniques for use with mass spectrometry have emerged in the past several years, and several have been investigated as a means for mass spectrometric read-out of planar separations. In this article, we review the atmospheric pressure surface sampling and ionization techniques that have been used for the read-out of planar separation media. For each technique, we briefly explain the operational basics and discuss the analyte type for which it is appropriate and some specific applications from the literature.

  12. FAST TRACK COMMUNICATION: Effects of Penning ionization on the discharge patterns of atmospheric pressure plasma jets

    NASA Astrophysics Data System (ADS)

    Li, Qing; Zhu, Wen-Chao; Zhu, Xi-Ming; Pu, Yi-Kang

    2010-09-01

    Atmospheric pressure plasma jets, generated in a coaxial dielectric barrier discharge configuration, have been investigated with different flowing gases. Discharge patterns in different tube regions were compared in the flowing gases of helium, neon and krypton. To explain the difference of these discharge patterns, a theoretical analysis is presented to reveal the possible basic processes. A comparison of experimental and theoretical results identifies that Penning ionization is mainly responsible for the discharge patterns of helium and neon plasma jets.

  13. An Open Port Sampling Interface for Liquid Introduction Atmospheric Pressure Ionization Mass Spectrometry

    SciTech Connect

    Van Berkel, Gary J.; Kertesz, Vilmos

    2015-08-25

    RATIONALE: A simple method to introduce unprocessed samples into a solvent for rapid characterization by liquid introduction atmospheric pressure ionization mass spectrometry has been lacking. The continuous flow, self-cleaning open port sampling interface introduced here fills this void. METHODS: The open port sampling interface used a vertically aligned, co-axial tube arrangement enabling solvent delivery to the sampling end of the device through the tubing annulus and solvent aspiration down the center tube and into the mass spectrometer ionization source via the commercial APCI emitter probe. The solvent delivery rate to the interface was set to exceed the aspiration rate creating a continuous sampling interface along with a constant, self-cleaning spillover of solvent from the top of the probe. RESULTS: Using the open port sampling interface with positive ion mode APCI and a hybrid quadrupole time of flight mass spectrometer, rapid, direct sampling and analysis possibilities are exemplified with plastics, ballpoint and felt tip ink pens, skin, and vegetable oils. These results demonstrated that the open port sampling interface could be used as a simple, versatile and self-cleaning system to rapidly introduce multiple types of unprocessed, sometimes highly concentrated and complex, samples into a solvent flow stream for subsequent ionization and analysis by mass spectrometry. The basic setup presented here could be incorporated with any self-aspirating liquid introduction ionization source (e.g., ESI, APCI, APPI, ICP, etc.) or any type of atmospheric pressure sampling ready mass spectrometer system. CONCLUSIONS: The open port sampling interface provides a means to introduce and quickly analyze unprocessed solid or liquid samples with liquid introduction atmospheric pressure ionization source without fear of sampling interface or ionization source contamination.

  14. An Open Port Sampling Interface for Liquid Introduction Atmospheric Pressure Ionization Mass Spectrometry

    SciTech Connect

    Van Berkel, Gary J.; Kertesz, Vilmos

    2015-01-01

    RATIONALE: A simple method to introduce unprocessed samples into a solvent for rapid characterization by liquid introduction atmospheric pressure ionization mass spectrometry has been lacking. The continuous flow, self-cleaning open port sampling interface introduced here fills this void. METHODS: The open port sampling interface used a vertically aligned, co-axial tube arrangement enabling solvent delivery to the sampling end of the device through the tubing annulus and solvent aspiration down the center tube and into the mass spectrometer ionization source via the commercial APCI emitter probe. The solvent delivery rate to the interface was set to exceed the aspiration rate creating a continuous sampling interface along with a constant, self-cleaning spillover of solvent from the top of the probe. RESULTS: Using the open port sampling interface with positive ion mode APCI and a hybrid quadrupole time of flight mass spectrometer, rapid, direct sampling and analysis possibilities are exemplified with plastics, ballpoint and felt tip ink pens, skin, and vegetable oils. These results demonstrated that the open port sampling interface could be used as a simple, versatile and self-cleaning system to rapidly introduce multiple types of unprocessed, sometimes highly concentrated and complex, samples into a solvent flow stream for subsequent ionization and analysis by mass spectrometry. The basic setup presented here could be incorporated with any self-aspirating liquid introduction ionization source (e.g., ESI, APCI, APPI, ICP, etc.) or any type of atmospheric pressure sampling ready mass spectrometer system. CONCLUSIONS: The open port sampling interface provides a means to introduce and quickly analyze unprocessed solid or liquid samples with liquid introduction atmospheric pressure ionization source without fear of sampling interface or ionization source contamination.

  15. An Open Port Sampling Interface for Liquid Introduction Atmospheric Pressure Ionization Mass Spectrometry

    DOE PAGESBeta

    Van Berkel, Gary J.; Kertesz, Vilmos

    2015-01-01

    RATIONALE: A simple method to introduce unprocessed samples into a solvent for rapid characterization by liquid introduction atmospheric pressure ionization mass spectrometry has been lacking. The continuous flow, self-cleaning open port sampling interface introduced here fills this void. METHODS: The open port sampling interface used a vertically aligned, co-axial tube arrangement enabling solvent delivery to the sampling end of the device through the tubing annulus and solvent aspiration down the center tube and into the mass spectrometer ionization source via the commercial APCI emitter probe. The solvent delivery rate to the interface was set to exceed the aspiration rate creatingmore » a continuous sampling interface along with a constant, self-cleaning spillover of solvent from the top of the probe. RESULTS: Using the open port sampling interface with positive ion mode APCI and a hybrid quadrupole time of flight mass spectrometer, rapid, direct sampling and analysis possibilities are exemplified with plastics, ballpoint and felt tip ink pens, skin, and vegetable oils. These results demonstrated that the open port sampling interface could be used as a simple, versatile and self-cleaning system to rapidly introduce multiple types of unprocessed, sometimes highly concentrated and complex, samples into a solvent flow stream for subsequent ionization and analysis by mass spectrometry. The basic setup presented here could be incorporated with any self-aspirating liquid introduction ionization source (e.g., ESI, APCI, APPI, ICP, etc.) or any type of atmospheric pressure sampling ready mass spectrometer system. CONCLUSIONS: The open port sampling interface provides a means to introduce and quickly analyze unprocessed solid or liquid samples with liquid introduction atmospheric pressure ionization source without fear of sampling interface or ionization source contamination.« less

  16. Atmospheric Pressure Ionization Permanent Magnet Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    PubMed Central

    Vilkov, Andrey N.; Gamage, Chaminda M.; Misharin, Alexander S.; Doroshenko, Vladimir M.; Tolmachev, Dmitry A.; Tarasova, Irina A.; Kharybin, Oleg N.; Novoselov, Konstantin P.; Gorshkov, Michael V.

    2007-01-01

    A new Fourier Transform Ion Cyclotron Resonance mass spectrometer based on a permanent magnet with an atmospheric pressure ionization source was designed and constructed. A mass resolving power (full-width-at-half-maximum) of up to 80,000 in the electron ionization mode and 25,000 in the electrospray mode was obtained. Also, a mass measurement accuracy at low-ppm level has been demonstrated for peptide mixtures in a mass range of up to 1,200 m/z in the isotopically resolved mass spectra. PMID:17587594

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  18. Understanding the flowing atmospheric-pressure afterglow (FAPA) ambient ionization source through optical means.

    PubMed

    Shelley, Jacob T; Chan, George C-Y; Hieftje, Gary M

    2012-02-01

    The advent of ambient desorption/ionization mass spectrometry (ADI-MS) has led to the development of a large number of atmospheric-pressure ionization sources. The largest group of such sources is based on electrical discharges; yet, the desorption and ionization processes that they employ remain largely uncharacterized. Here, the atmospheric-pressure glow discharge (APGD) and afterglow of a helium flowing atmospheric-pressure afterglow (FAPA) ionization source were examined by optical emission spectroscopy. Spatial emission profiles of species created in the APGD and afterglow were recorded under a variety of operating conditions, including discharge current, electrode polarity, and plasma-gas flow rate. From these studies, it was found that an appreciable amount of atmospheric H(2)O vapor, N(2), and O(2) diffuses through the hole in the plate electrode into the discharge to become a major source of reagent ions in ADI-MS analyses. Spatially resolved plasma parameters, such as OH rotational temperature (T(rot)) and electron number density (n(e)), were also measured in the APGD. Maximum values for T(rot) and n(e) were found to be ~1100 K and ~4×10(19) m(-3), respectively, and were both located at the pin cathode. In the afterglow, rotational temperatures from OH and N(2)(+) yielded drastically different values, with OH temperatures matching those obtained from infrared thermography measurements. The higher N(2)(+) temperature is believed to be caused by charge-transfer ionization of N(2) by He(2)(+). These findings are discussed in the context of previously reported ADI-MS analyses with the FAPA source. PMID:22125181

  19. High-resolution atmospheric pressure infrared laser desorption/ionization mass spectrometry imaging of biological tissue.

    PubMed

    Römpp, Andreas; Schäfer, Karl Christian; Guenther, Sabine; Wang, Zheng; Köstler, Martin; Leisner, Arne; Paschke, Carmen; Schramm, Thorsten; Spengler, Bernhard

    2013-09-01

    An atmospheric pressure laser desorption/ionization mass spectrometry imaging ion source has been developed that combines high spatial resolution and high mass resolution for the in situ analysis of biological tissue. The system is based on an infrared laser system working at 2.94 to 3.10 μm wavelength, employing a Nd:YAG laser-pumped optical parametrical oscillator. A Raman-shifted Nd:YAG laser system was also tested as an alternative irradiation source. A dedicated optical setup was used to focus the laser beam, coaxially with the ion optical axis and normal to the sample surface, to a spot size of 30 μm in diameter. No additional matrix was needed for laser desorption/ionization. A cooling stage was developed to reduce evaporation of physiological cell water. Ions were formed under atmospheric pressure and transferred by an extended heated capillary into the atmospheric pressure inlet of an orbital trapping mass spectrometer. Various phospholipid compounds were detected, identified, and imaged at a pixel resolution of up to 25 μm from mouse brain tissue sections. Mass accuracies of better than 2 ppm and a mass resolution of 30,000 at m/z = 400 were achieved for these measurements. PMID:23877173

  20. The Townsend coefficient of ionization in atmospheric pressure rare gas plasma

    NASA Astrophysics Data System (ADS)

    Zvereva, G.

    2015-12-01

    In the work the influence of the processes characteristic for atmospheric pressure heavy inert gases discharge plasma on the value of the first Townsend ionization coefficient were investigated. Krypton plasma was considered. Calculations have shown that the greatest impact on the value of the first Townsend ionization coefficient has dissociative recombination of molecular ions, followed by descending influence processes occur: stepwise ionization, the electron-electron collisions and superelastic ones. The effect of these processes begins to appear at concentrations of electrons and excited particles higher than 1012 cm-3. At times shorter than the time of molecular ions formation, when dissociative recombination is absent, should expect a significant increase of the ionization coefficient.

  1. Understanding the atmospheric pressure ionization of petroleum components: The effects of size, structure, and presence of heteroatoms.

    PubMed

    Huba, Anna Katarina; Huba, Kristina; Gardinali, Piero R

    2016-10-15

    Understanding the composition of crude oil and its changes with weathering is essential when assessing its provenience, fate, and toxicity. High-resolution mass spectrometry (HRMS) has provided the opportunity to address the complexity of crude oil by assigning molecular formulae, and sorting compounds into "classes" based on heteroatom content. However, factors such as suppression effects and discrimination towards certain components severely limit a truly comprehensive mass spectrometric characterization, and, despite the availability of increasingly better mass spectrometers, a complete characterization of oil still represents a major challenge. In order to fully comprehend the significance of class abundances, as well as the nature and identity of compounds detected, a good understanding of the ionization efficiency of the various compound classes is indispensable. The current study, therefore, analyzed model compounds typically found in crude oils by high-resolution mass spectrometry with atmospheric pressure photoionization (APPI), atmospheric pressure chemical ionization (APCI), and electrospray ionization (ESI), in order to provide a better understanding of benefits and drawbacks of each source. The findings indicate that, overall, APPI provides the best results, being able to ionize the broadest range of compounds, providing the best results with respect to ionization efficiencies, and exhibiting the least suppression effects. However, just like in the other two sources, in APPI several factors have shown to affect the ionization efficiency of petroleum model compounds. The main such factor is the presence or absence of functional groups that can be easily protonated/deprotonated, in addition to other factors such as size, methylation level, presence of heteroatoms, and ring structure. Overall, this study evidences the intrinsic limitations and benefits of each of the three sources, and should provide the fundamental knowledge required to expand the power

  2. Ion/molecule reaction and ion evaporation in atmospheric pressure spray ionization

    NASA Astrophysics Data System (ADS)

    Hirabayashi, Atsumu; Takada, Yasuaki; Kambara, Hideki; Umemura, Yuta; Ohta, Hitoshi; Ito, Haruhiko; Kuchitsu, Kozo

    1992-12-01

    The positive ions produced in atmospheric pressure spray ionization of ammonia, alanine and sucrose in aqueous solution were detected with a double-focusing mass spectrometer. The relative intensities of the quasi-molecular ions of ammonia, NH+4 (H2O)n (n = 0-3), were found to be proportional to the concentration of the ammonia solution and to increase with increasing distance d between the nozzle tip and the sample aperture of the mass spectrometer; this observation shows that the ammonia molecule is produced by the spray and is protonated at atmospheric pressure by a proton transfer reaction with the hydronium ion and its hydrated clusters. The observed dependences of the relative intensities of the protonated alanine molecules from alanine solution and the cationized sucrose molecules from sucrose solution on d show that some part of these quasi-molecular ions are also produced by the ion/molecule reaction in the gas phase. However, their dependences on the concentration, which are steeper than that in the ammonia case, indicate that a significant proportion of these ions are produced by ion evaporation from a droplet or liquid.

  3. Electron density and temperature measurement by continuum radiation emitted from weakly ionized atmospheric pressure plasmas

    SciTech Connect

    Park, Sanghoo; Choe, Wonho; Youn Moon, Se; Park, Jaeyoung

    2014-02-24

    The electron-atom neutral bremsstrahlung continuum radiation emitted from weakly ionized plasmas is investigated for electron density and temperature diagnostics. The continuum spectrum in 450–1000 nm emitted from the argon atmospheric pressure plasma is found to be in excellent agreement with the neutral bremsstrahlung formula with the electron-atom momentum transfer cross-section given by Popović. In 280–450 nm, however, a large discrepancy between the measured and the neutral bremsstrahlung emissivities is observed. We find that without accounting for the radiative H{sub 2} dissociation continuum, the temperature, and density measurements would be largely wrong, so that it should be taken into account for accurate measurement.

  4. Simultaneous extraction of acetylsalicylic acid and salicylic acid from human plasma and simultaneous estimation by liquid chromatography and atmospheric pressure chemical ionization/tandem mass spectrometry detection. Application to a pharmacokinetic study.

    PubMed

    Nirogi, Ramakrishna; Kandikere, Vishwottam; Mudigonda, Koteshwara; Ajjala, Devender; Suraneni, Ramakrishna; Thoddi, Parthasarathi

    2011-01-01

    A simple analytical method using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in atmospheric chemical ionization mode (APCI) for the simultaneous estimation of acetylsalicylic acid (ASA, CAS 50-78-2) and its active metabolite salicylic acid (SA, CAS 69-72-7) in human plasma has been developed and validated. ASA and SA were analyzed simultaneously despite differences in plasma concentration ranges of ASA and SA after oral administration of ASA. In spite of having different chemical, ionization and chromatographic properties, ASA and SA were extracted simultaneously from the plasma sample using acetonitrile protein precipitation followed by liquid-liquid extraction. The analytes were separated on a reversed phase column with rapid gradient program using mobile phase consisting of ammonium acetate buffer and methanol. The structural analogue diclofenac was used as an internal standard. The multiple reaction monitoring (MRM) transitions m/z 179 --> 137 for ASA, m/z 137 --> 65 for SA and m/z 294 --> 250 for IS were used. The assay exhibited a linear dynamic range of 0.02-10 microg/mL for ASA and 0.1-50 microg/mL for SA. The between-batch precision (%CV) ranged from 2.1 to 7.9% for ASA and from 0.2 to 5.2% for SA. The between-batch accuracy ranged from 95.4 to 96.7% for ASA and from 94.6 to 111.3% for SA. The validated method was successfully applied for the evaluation of pharmacokinetics of ASA after single oral administration of 650 mg test formulation versus two 325 mg reference formulations of ASA in human subjects. PMID:21755814

  5. Extractive Atmospheric Pressure Photoionization (EAPPI) Mass Spectrometry: Rapid Analysis of Chemicals in Complex Matrices

    NASA Astrophysics Data System (ADS)

    Liu, Chengyuan; Yang, Jiuzhong; Wang, Jian; Hu, Yonghua; Zhao, Wan; Zhou, Zhongyue; Qi, Fei; Pan, Yang

    2016-07-01

    Extractive atmospheric pressure photoionization (EAPPI) mass spectrometry was designed for rapid qualitative and quantitative analysis of chemicals in complex matrices. In this method, an ultrasonic nebulization system was applied to sample extraction, nebulization, and vaporization. Mixed with a gaseous dopant, vaporized analytes were ionized through ambient photon-induced ion-molecule reactions, and were mass-analyzed by a high resolution time-of-flight mass spectrometer (TOF-MS). After careful optimization and testing with pure sample solution, EAPPI was successfully applied to the fast screening of capsules, soil, natural products, and viscous compounds. Analysis was completed within a few seconds without the need for preseparation. Moreover, the quantification capability of EAPPI for matrices was evaluated by analyzing six polycyclic aromatic hydrocarbons (PAHs) in soil. The correlation coefficients (R 2 ) for standard curves of all six PAHs were above 0.99, and the detection limits were in the range of 0.16-0.34 ng/mg. In addition, EAPPI could also be used to monitor organic chemical reactions in real time.

  6. A novel APPI-MS setup for in situ degradation product studies of atmospherically relevant compounds: capillary atmospheric pressure photo ionization (cAPPI).

    PubMed

    Kersten, Hendrik; Derpmann, Valerie; Barnes, Ian; Brockmann, Klaus J; O'Brien, Rob; Benter, Thorsten

    2011-11-01

    We report on the development of a novel atmospheric pressure photoionization setup and its applicability for in situ degradation product studies of atmospherically relevant compounds. A custom miniature spark discharge lamp was embedded into an ion transfer capillary, which separates the atmospheric pressure from the low pressure region in the first differential pumping stage of a conventional atmospheric pressure ionization mass spectrometer. The lamp operates with a continuous argon flow and produces intense light emissions in the VUV. The custom lamp is operated windowless and efficiently illuminates the sample flow through the transfer capillary on an area smaller than 1 mm(2). Limits of detection in the lower ppbV range, a temporal resolution of milliseconds in the positive as well as the quasi simultaneously operating negative ion mode, and a significant reduction of ion transformation processes render this system applicable to real time studies of rapidly changing chemical systems. The method termed capillary atmospheric pressure photo ionization (cAPPI) is characterized with respect to the lamp emission properties as a function of the operating conditions, temporal response, and its applicability for in situ degradation product studies of atmospherically relevant compounds, respectively. PMID:21952756

  7. Femtosecond laser ablation particle introduction to a liquid sampling-atmospheric pressure glow discharge ionization source

    SciTech Connect

    Carado, Anthony J.; Quarles, C. Derrick; Duffin, Andrew M.; Barinaga, Charles J.; Russo, Richard E.; Marcus, R. Kenneth; Eiden, Gregory C.; Koppenaal, David W.

    2012-01-01

    This work describes the use of a compact, liquid sampling – atmospheric pressure glow discharge (LS-APGD) ionization source to ionize metal particles within a laser ablation aerosol. Mass analysis was performed with a Thermo Scientific Exactive Mass Spectrometer which utilizes an orbitrap mass analyzer capable of producing mass resolution exceeding M/ΔM > 160,000. The LS-APGD source generates a low-power plasma between the surface of an electrolytic solution flowing at several µl min-1 through a fused silica capillary and a counter electrode consisting of a stainless steel capillary employed to deliver the laser ablation particles into the plasma. Sample particles of approximately 100 nm were generated with an Applied Spectra femtosecond laser located remotely and transported through 25 meters of polyurethane tubing by means of argon carrier gas. Samples consisted of an oxygen free copper shard, a disk of solder, and a one-cent U.S. coin. Analyte signal onset was readily detectable relative to the background signal produced by the carrier gas alone. The high mass resolution capability of the orbitrap mass spectrometer was demonstrated on the solder sample with resolution exceeding 90,000 for Pb and 160,000 for Cu. In addition, results from a laser ablation depth-profiling experiment of a one cent coin revealed retention of the relative locations of the ~10 µm copper cladding and zinc rich bulk layers.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  9. Decontamination of chemical and biological warfare (CBW) agents using an atmospheric pressure plasma jet (APPJ)

    SciTech Connect

    Herrmann, H.W.; Henins, I.; Park, J.; Selwyn, G.S.

    1999-05-01

    The atmospheric pressure plasma jet (APPJ) [A. Sch{umlt u}tze {ital et al.}, IEEE Trans. Plasma Sci. {bold 26}, 1685 (1998)] is a nonthermal, high pressure, uniform glow plasma discharge that produces a high velocity effluent stream of highly reactive chemical species. The discharge operates on a feedstock gas (e.g., He/O{sub 2}/H{sub 2}O), which flows between an outer, grounded, cylindrical electrode and an inner, coaxial electrode powered at 13.56 MHz rf. While passing through the plasma, the feedgas becomes excited, dissociated or ionized by electron impact. Once the gas exits the discharge volume, ions and electrons are rapidly lost by recombination, but the fast-flowing effluent still contains neutral metastable species (e.g., O{sub 2}{sup {asterisk}}, He{sup {asterisk}}) and radicals (e.g., O, OH). This reactive effluent has been shown to be an effective neutralizer of surrogates for anthrax spores and mustard blister agent. Unlike conventional wet decontamination methods, the plasma effluent does not cause corrosion and it does not destroy wiring, electronics, or most plastics, making it highly suitable for decontamination of sensitive equipment and interior spaces. Furthermore, the reactive species in the effluent rapidly degrade into harmless products leaving no lingering residue or harmful by-products. {copyright} {ital 1999 American Institute of Physics.}

  10. Decontamination of Chemical/Biological Warfare (CBW) Agents Using an Atmospheric Pressure Plasma Jet (APPJ)

    NASA Astrophysics Data System (ADS)

    Herrmann, Hans W.

    1998-11-01

    The atmospheric pressure plasma jet (APPJ) is a non-thermal, high pressure, uniform glow discharge that produces a high velocity effluent stream of highly reactive chemical species. The discharge operates on a feedstock gas (e.g. He/O_2/H_2O) which flows between an outer, grounded, cylindrical electrode and an inner, coaxial electrode powered at 13.56 MHz RF. While passing through the plasma, the feedgas becomes excited, dissociated or ionized by electron impact. Once the gas exits the discharge volume, ions and electrons are rapidly lost by recombination, but the fast-flowing effluent still contains metastables (e.g. O2*, He*) and radicals (e.g. O, OH). These reactive species have been shown to be effective neutralizers of surrogates for anthrax spores, mustard blister agent and VX nerve gas. Unlike conventional, wet decontamination methods, the plasma effluent does not cause corrosion of most surfaces and does not damage wiring, electronics, nor most plastics. This makes it highly suitable for decontamination of high value sensitive equipment such as is found in vehicle interiors (i.e. tanks, planes...) for which there is currently no good decontamination technique. Furthermore, the reactive species rapidly degrade into harmless products leaving no lingering residue or harmful byproducts. Physics of the APPJ will be discussed and results of surface decontamination experiments using simulant and actual CBW agents will be presented.

  11. Study of atmospheric pressure weakly ionized plasma as surface compatibilization technique for improved plastic composites loaded with cellulose based fillers

    NASA Astrophysics Data System (ADS)

    Lekobou, William Pimakouon

    Atmospheric pressure plasmas have gained considerable interest from researchers recently for their unique prospective of engineering surfaces with plasma without the need of vacuum systems. They offer the advantage of low energy consumption, minimal capital cost and their simplicity as compared to conventional low pressure plasmas make them easy to upscale from laboratory to industry size. The present dissertation summarizes results of our attempt at applying atmospheric pressure weakly ionized plasma (APWIP) to the engineering of plastic composites filled with cellulose based substrates. An APWIP reactor was designed and built based on a multipoint-to-grounded ring and screen configurations. The carrier gas was argon and acetylene serves as the precursor molecule. The APWIP reactors showed capability of depositing plasma polymerized coating rich in carbon on substrates positioned within the electrode gap as well as downstream of the plasma discharge into the afterglow region. Our findings show that films grow by forming islands which for prolonged deposition time grow into thin films showing nodules, aggregates of nodules and microspheres. They also show chemical structure similar to films deposited from hydrocarbons with other conventional plasma techniques. The plasma polymerized deposits were used on substrates to modify their surface properties. Results show the surface of wood veneer and wood flour can be finely tuned from hydrophilic to hydrophobic. It was achieved by altering the topography of the surfaces along with their chemical composition. The wettability of wood veneer was investigated with contact angle measurements on capacitive drops and the capillary effect was utilized to assess surface properties of wood flour exposed to the discharges.

  12. Determination of nitrogen monoxide in high purity nitrogen gas with an atmospheric pressure ionization mass spectrometer

    NASA Technical Reports Server (NTRS)

    Kato, K.

    1985-01-01

    An atmospheric pressure ionization mass spectrometric (API-MS) method was studied for the determination of residual NO in high purity N2 gas. The API-MS is very sensitive to NO, but the presence of O2 interferes with the NO measurement. Nitrogen gas in cylinders as sample gas was mixed with NO standard gas and/or O2 standard gas, and then introduced into the API-MS. The calibration curves of NO and O2 has linearity in the region of 0 - 2 ppm, but the slopes changed with every cylinder. The effect of O2 on NO+ peak was additive and proportional to O2 concentration in the range of 0 - 0.5 ppm. The increase in NO+ intensity due to O2 was (0.07 - 0.13)%/O2, 1 ppm. Determination of NO and O2 was carried out by the standard addition method to eliminate the influence of variation of slopes. The interference due to O2 was estimated from the product of the O2 concentration and the ratio of slope A to Slope B. Slope A is the change in the NO+ intensity with the O2 concentration. Slope B is the intensity with O2 concentration.

  13. Microfluidic Chip Coupled with Thermal Desorption Atmospheric Pressure Ionization Mass Spectrometry

    PubMed Central

    Chang, Chia-Hsien; Chen, Tsung-Yi; Chen, Yu-Chie

    2014-01-01

    Microfluidic chips have been used as platforms for a diversity of research purposes such as for separation and micro-reaction. One of the suitable detectors for microfluidic chip is mass spectrometry. Because microfluidic chips are generally operated in an open air condition, mass spectrometry coupled with atmospheric pressure ion sources can suit the requirement with minimum compromise. In this study, we develop a new interface to couple a microfluidic chip with mass spectrometry. A capillary tip coated with a layer of graphite, capable of absorbing energy of near-infrared (NIR) light is used to interface microfluidic chip with mass spectrometry. An NIR laser diode (λ=808 nm) is used to irradiate the capillary tip for assisting the generation of spray from the eluent of the microfluidic chip. An electrospray is provided to fuse with the spray generated from the microfluidic chip for post-ionization. Transesterification is used as the example to demonstrate the feasibility of using this interface to couple microfluidic chip with mass spectrometry. PMID:26839753

  14. The Protonation Site of para-Dimethylaminobenzoic Acid Using Atmospheric Pressure Ionization Methods

    NASA Astrophysics Data System (ADS)

    Chai, Yunfeng; Weng, Guofeng; Shen, Shanshan; Sun, Cuirong; Pan, Yuanjiang

    2015-04-01

    The protonation site of para-dimethylaminobenzoic acid ( p-DMABA) was investigated using atmospheric pressure ionization methods (ESI and APCI) coupled with collision-induced dissociation (CID), nuclear magnetic resonance (NMR), and computational chemistry. Theoretical calculations and NMR experiments indicate that the dimethyl amino group is the preferred site of protonation both in the gas phase and aqueous solution. Protonation of p-DMABA occurs at the nitrogen atom by ESI independent of the solvents and other operation conditions under typical thermodynamic control. However, APCI produces a mixture of the nitrogen- and carbonyl oxygen-protonated p-DMABA when aprotic organic solvents (acetonitrile, acetone, and tetrahydrofuran) are used, exhibiting evident kinetic characteristics of protonation. But using protic organic solvents (methanol, ethanol, and isopropanol) in APCI still leads to the formation of thermodynamically stable N-protonated p-DMABA. These structural assignments were based on the different CID behavior of the N- and O-protonated p-DMABA. The losses of methyl radical and water are the diagnostic fragmentations of the N- and O-protonated p-DMABA, respectively. In addition, the N-protonated p-DMABA is more stable than the O-protonated p-DMABA in CID revealed by energy resolved experiments and theoretical calculations.

  15. Back corona enhanced organic film deposition inside an Atmospheric Pressure Weakly Ionized Plasma reactor

    NASA Astrophysics Data System (ADS)

    Islam, Rokibul; Xie, Shuzheng; Englund, Karl; Pedrow, Patrick

    2014-10-01

    A grounded screen with short needle-like protrusions has been designed to generate back corona in an Atmospheric Pressure Weakly Ionized Plasma (APWIP) reactor. The grounded screen with protrusions is placed downstream at a variable gap length from an array of needles that is energized with 60 Hz high voltage. The excitation voltage is in the range 0--10 kV RMS and the feed gas mixture consists of argon and acetylene. A Lecroy 9350AL 500 MHz digital oscilloscope is used to monitor the reactor voltage and current using a resistive voltage divider and a current viewing resistor, respectively. The current signal contains many positive and negative current pulses associated with corona discharge. Analysis of the current signal shows asymmetry between positive and negative corona discharge currents. Photographs show substantial back corona generated near the tips of the protrusions situated at the grounded screen. The back corona activates via bond scission acetylene radicals that are transported downstream to form a plasma-polymerized film on a substrate positioned downstream from the grounded screen. The oscillograms will be used to generate corona mode maps that show the nature of the corona discharge as a function of gap spacing, applied voltage and many other reactor parameters.

  16. Effects of easily ionizable elements on the liquid sampling atmospheric pressure glow discharge

    NASA Astrophysics Data System (ADS)

    Venzie, Jacob L.; Marcus, R. Kenneth

    2006-06-01

    A series of studies has been undertaken to determine the susceptibility of the liquid sampling-atmospheric pressure glow discharge (LS-APGD) atomic emission source to easily ionizable element (EIE) effects. The initial portions of the study involved monitoring the voltage drop across the plasma as a function of the pH to ascertain whether or not the conductivity of the liquid eluent alters the plasma energetics and subsequently the analyte signal strength. It was found that altering the pH (0.0 to 2.0) in the sample matrix did not significantly change the discharge voltage. The emission signal intensities for Cu(I) 327.4 nm, Mo(I) 344.7 nm, Sc(I) 326.9 nm and Hg(I) 253.6 nm were measured as a function of the easily ionizable element (sodium and calcium) concentration in the injection matrix. A range of 0.0 to 0.1% (w/v) EIE in the sample matrix did not cause a significant change in the Cu, Sc, and Mo signal-to-background ratios, with only a slight change noted for Hg. In addition to this test of analyte response, the plasma energetics as a function of EIE concentration are assessed using the ratio of Mg(II) to Mg(I) (280.2 nm and 285.2 nm, respectively) intensities. The Mg(II)/Mg(I) ratio showed that the plasma energetics did not change significantly over the same range of EIE addition. These results are best explained by the electrolytic nature of the eluent acting as an ionic (and perhaps spectrochemical) buffer.

  17. Probe electrospray ionization (PESI) mass spectrometry with discontinuous atmospheric pressure interface (DAPI).

    PubMed

    Hiraoka, Kenzo; Usmanov, Dilshadbek T; Chen, Lee Chuin; Ninomiya, Satoshi; Mandal, Mridul K; Saha, Subhrakanti

    2015-01-01

    Probe electrospray ionization (PESI) using a 0.2 mm outside diameter titanium wire was performed and the generated ions were introduced into the mass spectrometer via a discontinuous atmospheric pressure interface using a pinch valve. Time-lapse PESI mass spectra were acquired by gradually increasing delay time for the pinch valve opening with respect to the start of each electrospray event when a high voltage was applied. The opening time of the pinch valve was 20 ms. Time-resolved PESI mass spectra showed marked differences for 10 mM NaCl, 10(-5) M gramicidin S and insulin in H(2)O/CH(3)OH/CH(3)COOH/CH(3)COONH(4) (65/35/1) with and without the addition of 10 mM CH(3)COONH(4). This was ascribed to the pH change of the liquid attached to the needle caused by electrochemical reactions taking place at the interface between the metal probe and the solution. NaCl cluster ions appeared only after the depletion of analytes. For the mixed solution of 10(-5) M cytochrome c, insulin, and gramicidin S in H(2)O/CH(3)OH/CH(3)COOH (65/35/1), a sequential appearance of analyte ions in the order of cytochrome c→insulin→gramicidin S was observed. The present technique was applied to three narcotic samples; methamphetamine, morphine and codeine. Limits of detection for these compounds were 10 ppb in H(2)O/CH(3)OH (1/1) for the single sampling with a pinch valve opening time of 200 ms. PMID:26307713

  18. Determination of dextromethorphan and its metabolite dextrorphan in human urine using high performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry: a study of selectivity of a tandem mass spectrometric assay.

    PubMed

    Constanzer, M L; Chavez-Eng, C M; Fu, I; Woolf, E J; Matuszewski, B K

    2005-02-25

    Analytical method for the simultaneous determination of dextromethorphan (1) and dextrorphan (2) in urine, based on solid-phase extraction of drug from acidified hydrolyzed biological matrix, were developed. The analytes (1 and 2) and the internal standard (levallorphan, 3, IS) were detected by high-performance liquid chromatography-mass spectrometry (HPLC-MS/MS) in positive ionization mode using a heated nebulizer (HN) probe and monitoring their precursor-->product ion combinations of m/z 272-->215, 258-->201, and 284-->201 for 1, 2, and 3, respectively, in multiple reaction monitoring mode. The analytes and IS were chromatographed on a Keystone Prism reverse phase (50 mm x 2.0 mm) 5 microm column using a mobile phases consisting of a 35/65 or 27/73 mixtures of methanol/water containing 0.1% TFA adjusted to pH 3 with ammonium hydroxide pumped at 0.4 ml/min for 1 and 2, respectively. The limits of reliable quantification of 1 and 2 were 2 and 250 ng/ml, respectively, when 1 ml of urine was processed. The absence of matrix effect was demonstrated by analysis of neat standards and standards spiked into urine extracts originating from five different sources. The linear ranges of the assay were 2-200 and 250-20,000 ng/ml for 1 and 2, respectively. Assay selectivity was evaluated by monitoring the "cross-talk" effects from other metabolites into the MS/MS channels used for monitoring 1, 2, and 3. In addition, an interfering peak originating from an unknown metabolite of 1 into the quantification of dextromethorphan was detected, requiring an effective chromatographic separation of analytes from other metabolites of 1. The need for careful assessment of selectivity of the HPLC-MS/MS assay in the presence of metabolites, and the assessment of matrix effect, are emphasized. PMID:15664362

  19. A new multiplex method for the diagnosis of peroxisomal disorders allowing simultaneous determination of plasma very-long-chain fatty acids, phytanic, pristanic, docosahexaenoic and bile acids by high-performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Semeraro, Michela; Rizzo, Cristiano; Boenzi, Sara; Cappa, Marco; Bertini, Enrico; Antonetti, Giacomo; Dionisi-Vici, Carlo

    2016-07-01

    Peroxisomal disorders (PDs) present with wide phenotypic variability. An appropriate diagnosis requires a complete analysis of peroxisomal metabolites. We developed a multiplex LC-MS/MS method, using atmospheric pressure chemical ionization allowing the simultaneous determination in plasma of very-long-chain fatty acids, phytanic, pristanic, docosahexaenoic acids and di- and tri-hydroxycolestanoic bile acids. Two hundred microliters of plasma extracted with acetonitrile and 200μl extracted with hexane after an acid hydrolysis were combined, evaporated, dissolved in 10μl of methanol and analyzed. The acquisition was in negative-ion mode using multiple reaction monitoring. The method was validated analytically and clinically. Linearity was 0.1-200μmol/l for docosanoic, cis-13-docosenoic, tetracosanoic, cis-15-tetracosenoic and phytanic acids; 0.01-10μmol/l for hexacosanoic acid; 0.02-20μmol/l for di-hydroxycolestanoic, tri-hydroxycolestanoic and pristanic acids; 0.3-300μmol/l for docosahexaenoic acid. Intra-day and inter-day CVs were below 3.88 and 3.98 respectively for all compounds. Samples from patients with known peroxisomal disorders were compared with controls and the method allowed to confirm the diagnosis in all subjects with a 100% sensitivity. The advantage of this multiplex method is to allow in a single chromatographic run the simultaneous determination of a large number of peroxisome biomarkers with a simple preparative phase without derivatization. PMID:27189059

  20. Surface chemical changes of atmospheric pressure plasma treated rabbit fibres important for felting process

    NASA Astrophysics Data System (ADS)

    Štěpánová, Vlasta; Slavíček, Pavel; Stupavská, Monika; Jurmanová, Jana; Černák, Mirko

    2015-11-01

    We introduce the atmospheric pressure plasma treatment as a suitable procedure for in-line industrial application of rabbit fibres pre-treatment. Changes of rabbit fibre properties due to the plasma treatment were studied in order to develop new technology of plasma-based treatment before felting. Diffuse Coplanar Surface Barrier Discharge (DCSBD) in ambient air at atmospheric pressure was used for plasma treatment. Scanning electron microscopy was used for determination of the fibres morphology before and after plasma treatment. X-ray photoelectron spectroscopy and attenuated total reflectance-Fourier transform infrared spectroscopy were used for evaluation of reactive groups. The concentration of carbon decreased and conversely the concentration of nitrogen and oxygen increased after plasma treatment. Aging effect of plasma treated fibres was also investigated. Using Washburn method the significant increase of fibres wettability was observed after plasma treatment. New approach of pre-treatment of fibres before felting using plasma was developed. Plasma treatment of fibres at atmospheric pressure can replace the chemical method which consists of application of strong acids on fibres.

  1. What Is the Opposite of Pandora's Box? Direct Analysis, Ambient Ionization, and a New Generation of Atmospheric Pressure Ion Sources.

    PubMed

    B Cody, Robert

    2013-01-01

    The introduction of DART and DESI sources approximately seven years ago led to the development of a new series of atmospheric pressure ion sources referred to as "ambient ionization" sources. These fall into two major categories: spray techniques like DESI or plasma techniques like DART. The selectivity of "direct ionization," meaning analysis without chromatography and with little or no sample preparation, depends on the mass spectrometer selectivity. Although high resolution and tandem mass spectrometry are valuable tools, rapid and simple sample preparation methods can improve the utility of ambient ionization methods. The concept of ambient ionization has led to the realization that there are many more ways to form ions than might be expected. An interesting example is the use of a flint-and-steel spark source to generate ions from compounds such as phenolphthalein and Gramicidin S. PMID:24349926

  2. Atmospheric pressure chemical vapor deposition of CdTe—reactor design considerations

    NASA Astrophysics Data System (ADS)

    Meyers, Peter V.; Kee, Robert J.; Raja, Laxminarayan; Wolden, Colin A.; Aire, Michael

    1999-03-01

    Atmospheric Pressure Chemical Vapor Deposition (APCVD) of polycrystalline thin-film CdTe appears to offer several practical advantages over state-of-the-art manufacturing techniques. APCVD employs the same reaction chemistry utilized to produce 16% efficient CdTe cells (i.e., same reaction chemistry as Close Spaced Sublimation), avoids use of vacuum equipment, allows for physical separation of the source and substrate, and employs forced convection to ensure uniform delivery of source material over large-area substrates. Reactor design considerations and preliminary numerical simulations of mass transport are presented.

  3. Atmospheric-pressure ionization: New approaches and applications for plasmas in contact with liquids

    NASA Astrophysics Data System (ADS)

    Go, D. B.

    2015-10-01

    Historically, gas discharges have been difficult to stabilize at atmospheric pressure, and this has confined them to operation at low pressure under vacuum conditions. However, recent advances in plasma technology have enabled stable high pressure gas discharges up to and even exceeding atmospheric pressure. One significant advantage of operating at atmospheric pressure is that the plasma can be brought into contact with non-conventional substrates, especially soft materials such as plastics, biological tissue, and aqueous solutions. This last example is of prime interest as plasma/liquid interactions have a number of important implications in applications ranging from water purification to plasma medicine. In this paper, recent work studying the impact of electrons in the plasma inducing reactions in aqueous solutions is discussed. These studies include measurements of the bulk solution as the electrons induce long-lived species as well as interfacial measurements directly at the plasma/liquid interface to probe the behaviour of electrons traversing from the plasma into the liquid.

  4. Specific interaction between negative atmospheric ions and organic compounds in atmospheric pressure corona discharge ionization mass spectrometry.

    PubMed

    Sekimoto, Kanako; Sakai, Mami; Takayama, Mitsuo

    2012-06-01

    The interaction between negative atmospheric ions and various types of organic compounds were investigated using atmospheric pressure corona discharge ionization (APCDI) mass spectrometry. Atmospheric negative ions such as O(2)(-), HCO(3)(-), COO(-)(COOH), NO(2)(-), NO(3)(-), and NO(3)(-)(HNO(3)) having different proton affinities served as the reactant ions for analyte ionization in APCDI in negative-ion mode. The individual atmospheric ions specifically ionized aliphatic and aromatic compounds with various functional groups as atmospheric ion adducts and deprotonated analytes. The formation of the atmospheric ion adducts under certain discharge conditions is most likely attributable to the affinity between the analyte and atmospheric ion and the concentration of the atmospheric ion produced under these conditions. The deprotonated analytes, in contrast, were generated from the adducts of the atmospheric ions with higher proton affinity attributable to efficient proton abstraction from the analyte by the atmospheric ion. PMID:22528201

  5. Desorption/ionization of acrylamide in aqueous solutions in atmospheric pressure air using a microdischarge with vortex focusing of ions

    NASA Astrophysics Data System (ADS)

    Pervukhin, V. V.; Sheven', D. G.

    2014-09-01

    A method of desorption/ionization in a microdischarge with ion vortex focusing (vortex focusing microdischarge, VFM) is suggested. A glow microdischarge is initiated in an air flow, and resulting ions act on the surface of interest. As a model compound, an aqueous solution of acrylamide is taken. Desorption/ionization taking place under atmospheric pressure is followed by the mass-spectrometric identification of the ions. The operating parameters of the VFM system are studied and optimized. Upon optimization of the system, the detection limit of acrylamide trace amounts in aqueous solutions is determined using the suggested method of desorption/ionization and analyte ion focusing with a vortex (swirling) jet. The acrylamide detection limit is found to be 2 × 10-3 g/L.

  6. Aliphatic hydrocarbon spectra by helium ionization mass spectrometry (HIMS) on a modified atmospheric-pressure source designed for electrospray ionization.

    PubMed

    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 (C(44)H(90)), 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 D(2)O vapor in an HPIS-MS instrument confirmed that the proton donor for ionization of unsaturated hydrocarbons is protonated water. PMID:21953194

  7. Microcavity array plasma system for remote chemical processing at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Lee, Dae-Sung; Hamaguchi, Satoshi; Sakai, Osamu; Park, Sung-Jin; Eden, J. Gary

    2012-06-01

    A microplasma system designed for chemical processing at atmospheric pressure is fabricated and characterized with flowing He/O2 gas mixtures. At the heart of this microcavity dielectric barrier discharge (MDBD) system are two arrays of half-ellipsoidal microcavities engraved by micropowder blasting into dielectric surfaces facing a flowing, low-temperature plasma. Experiments demonstrate that the ignition voltage is reduced, and the spatially averaged optical emission is doubled, for an MDBD flowing plasma array relative to an equivalent system having no microcavities. As an example of the potential of flowing atmospheric microplasma systems for chemical processing, the decomposition of methylene blue (as evidenced by decoloration at 650.2 nm) is shown to proceed at a rate as much as a factor of two greater than that for a non-microcavity equivalent.

  8. Analysis of mass transport in an atmospheric pressure remote plasma-enhanced chemical vapor deposition process

    SciTech Connect

    Cardoso, R. P.; Belmonte, T.; Henrion, G.; Gries, T.; Tixhon, E.

    2010-01-15

    In remote microwave plasma enhanced chemical vapor deposition processes operated at atmospheric pressure, high deposition rates are associated with the localization of precursors on the treated surface. We show that mass transport can be advantageously ensured by convection for the heavier precursor, the lighter being driven by turbulent diffusion toward the surface. Transport by laminar diffusion is negligible. The use of high flow rates is mandatory to have a good mixing of species. The use of an injection nozzle with micrometer-sized hole enables us to define accurately the reaction area between the reactive species. The localization of the flow leads to high deposition rates by confining the reactive species over a small area, the deposition yield being therefore very high. Increasing the temperature modifies nonlinearly the deposition rates and the coating properties.

  9. Diamond synthesis at atmospheric pressure by microwave capillary plasma chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Hemawan, Kadek W.; Gou, Huiyang; Hemley, Russell J.

    2015-11-01

    Polycrystalline diamond has been synthesized on silicon substrates at atmospheric pressure, using a microwave capillary plasma chemical vapor deposition technique. The CH4/Ar plasma was generated inside of quartz capillary tubes using 2.45 GHz microwave excitation without adding H2 into the deposition gas chemistry. Electronically excited species of CN, C2, Ar, N2, CH, Hβ, and Hα were observed in the emission spectra. Raman measurements of deposited material indicate the formation of well-crystallized diamond, as evidenced by the sharp T2g phonon at 1333 cm-1 peak relative to the Raman features of graphitic carbon. Field emission scanning electron microscopy images reveal that, depending on the growth conditions, the carbon microstructures of grown films exhibit "coral" and "cauliflower-like" morphologies or well-facetted diamond crystals with grain sizes ranging from 100 nm to 10 μm.

  10. Influence of field emission on the propagation of cylindrical fast ionization wave in atmospheric-pressure nitrogen

    NASA Astrophysics Data System (ADS)

    Levko, Dmitry; Raja, Laxminarayan L.

    2016-04-01

    The influence of field emission of electrons from surfaces on the fast ionization wave (FIW) propagation in high-voltage nanosecond pulse discharge in the atmospheric-pressure nitrogen is studied by a one-dimensional Particle-in-Cell Monte Carlo Collisions model. A strong influence of field emission on the FIW dynamics and plasma parameters is obtained. Namely, the accounting for the field emission makes possible the bridging of the cathode-anode gap by rather dense plasma (˜1013 cm-3) in less than 1 ns. This is explained by the generation of runaway electrons from the field emitted electrons. These electrons are able to cross the entire gap pre-ionizing it and promoting the ionization wave propagation. We have found that the propagation of runaway electrons through the gap cannot be accompanied by the streamer propagation, because the runaway electrons align the plasma density gradients. In addition, we have obtained that the field enhancement factor allows controlling the speed of ionization wave propagation.

  11. Modeling chemical vapor deposition of silicon dioxide in microreactors at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Konakov, S. A.; Krzhizhanovskaya, V. V.

    2015-01-01

    We developed a multiphysics mathematical model for simulation of silicon dioxide Chemical Vapor Deposition (CVD) from tetraethyl orthosilicate (TEOS) and oxygen mixture in a microreactor at atmospheric pressure. Microfluidics is a promising technology with numerous applications in chemical synthesis due to its high heat and mass transfer efficiency and well-controlled flow parameters. Experimental studies of CVD microreactor technology are slow and expensive. Analytical solution of the governing equations is impossible due to the complexity of intertwined non-linear physical and chemical processes. Computer simulation is the most effective tool for design and optimization of microreactors. Our computational fluid dynamics model employs mass, momentum and energy balance equations for a laminar transient flow of a chemically reacting gas mixture at low Reynolds number. Simulation results show the influence of microreactor configuration and process parameters on SiO2 deposition rate and uniformity. We simulated three microreactors with the central channel diameter of 5, 10, 20 micrometers, varying gas flow rate in the range of 5-100 microliters per hour and temperature in the range of 300-800 °C. For each microchannel diameter we found an optimal set of process parameters providing the best quality of deposited material. The model will be used for optimization of the microreactor configuration and technological parameters to facilitate the experimental stage of this research.

  12. Minimally-Invasive Gene Transfection by Chemical and Physical Interaction of Atmospheric Pressure Plasma Flow

    NASA Astrophysics Data System (ADS)

    Kaneko, Toshiro

    2014-10-01

    Non-equilibrium atmospheric pressure plasma irradiated to the living-cell is investigated for medical applications such as gene transfection, which is expected to play an important role in molecular biology, gene therapy, and creation of induced pluripotent stem (iPS) cells. However, the conventional gene transfection using the plasma has some problems that the cell viability is low and the genes cannot be transferred into some specific lipid cells, which is attributed to the unknown mechanism of the gene transfection using the plasma. Therefore, the time-controlled atmospheric pressure plasma flow is generated and irradiated to the living-cell suspended solution for clarifying the transfection mechanism toward developing highly-efficient and minimally- invasive gene transfection system. In this experiment, fluorescent dye YOYO-1 is used as the simulated gene and LIVE/DEAD Stain is simultaneously used for cell viability assay. By the fluorescence image, the transfection efficiency is calculated as the ratio of the number of transferred and surviving cells to total cell count. It is clarified that the transfection efficiency is significantly increased by the short-time (<4 sec) and short-distance (<40 mm) plasma irradiation, and the high transfection efficiency of 53% is realized together with the high cell viability (>90%). This result indicates that the physical effects such as the electric field caused by the charged particles arriving at the surface of the cell membrane, and chemical effects associated with plasma-activated products in solution act synergistically to enhance the cell-membrane transport with low-damage. This work was supported by JSPS KAKENHI Grant Number 24108004.

  13. Digitally-multiplexed nanoelectrospray ionization atmospheric pressure drift tube ion mobility spectrometry.

    PubMed

    Kwasnik, Mark; Caramore, Joe; Fernández, Facundo M

    2009-02-15

    One of the shortcomings of atmospheric pressure drift tube ion mobility spectrometry (DTIMS) is its intrinsically low duty cycle (approximately 0.04-1%) caused by the rapid pulsing of the ion gate (25-400 micros) followed by a comparatively long drift time (25-100 ms), which translates into a loss of sensitivity. Multiplexing approaches via Hadamard and Fourier-type gating techniques have been reported for increasing the sensitivity of DTIMS. Here, we report an extended multiplexing approach which encompasses arbitrary binary ion injection waveforms with variable duty cycles ranging from 0.5 to 50%. In this approach, ion mobility spectra can be collected using conventional signal averaging, arbitrary, standard Hadamard and/or "extended" Hadamard operation modes. Initial results indicate signal-to-noise gains ranging from 2-7-fold for both arbitrary and "extended" Hadamard sequences. Standard Hadamard transform IMS provided increased sensitivity, with gains ranging from 9-12-fold, however, mobility spectra suffered from defects that appeared as false peaks, which were reduced or eliminated when using arbitrary or "extended" Hadamard waveforms for multiplexing. Digital multiplexing enables variation of the duty cycle in a continuous manner, minimizing the contribution of imperfect modulation on spectral defects without the need for complex spectral correction methods. By reducing the frequency of gating events employed in the variable duty cycle sequences, the contributions of factors such as ion depletion prior to gating, interaction of successively injected ion packets, and the cumulative effect of imperfect gating events were mitigated. PMID:19133785

  14. Studies of the mechanism of the cluster formation in a thermally sampling atmospheric pressure ionization mass spectrometer

    SciTech Connect

    Albrecht, Sascha Stroh, Fred; Klopotowski, Sebastian Derpmann, Valerie Klee, Sonja Brockmann, Klaus J. Benter, Thorsten

    2014-01-15

    In this study a thermally sampling atmospheric pressure ionization mass spectrometer is described and characterized. The ion transfer stage offers the capability to sample cluster ions at thermal equilibrium and during this transfer fundamental processes possibly affecting the cluster distribution are also readily identified. Additionally, the transfer stage combines optional collision-induced dissociation (CID) analysis of the cluster composition with thermal equilibrium sampling of clusters. The performance of the setup is demonstrated with regard to the proton-bound water cluster system. The benefit of the studied processes is that they can help to improve future transfer stages and to understand cluster ion reactions in ion mobility tubes and high-pressure ion sources. In addition, the instrument allows for the identification of fragmentation and protonation reactions caused by CID.

  15. COMSOL Modeling of Transport of Neutral Radicals to Substrate Surfaces Located Downstream from an Atmospheric Pressure Weakly Ionized Plasma Reactor

    NASA Astrophysics Data System (ADS)

    Islam, Rokibul; Lekobou, William; Wemlinger, Erik; Pedrow, Patrick

    2012-10-01

    An Atmospheric Pressure Weakly Ionized Plasma (APWIP) Reactor generates a significant number of charged particles and neutral radicals. In our work the carrier gas is argon and the precursor molecule is acetylene. The APWIP is generated by corona discharges associated with an array of high voltage metal needles facing a grounded metal screen. Neutral radical transport downstream from the grounded screen to the substrate via diffusion and convection will be modeled with COMSOL, a finite element software package. Substrates will include objects with various shapes and characteristic dimensions that range from nanometers to centimeters. After the model is validated against canonical problems with known solutions, thin film deposition rates will be compared with experimentally measured results. Substrate geometries will include discs, spheres, fibers and highly porous surfaces such as those found on asphalt road surfaces. A single generic neutral radical will be used to represent the entire family of neutral radicals resulting from acetylene bond scission by free electron impact.

  16. Studies of the mechanism of the cluster formation in a thermally sampling atmospheric pressure ionization mass spectrometer.

    PubMed

    Albrecht, Sascha; Klopotowski, Sebastian; Derpmann, Valerie; Klee, Sonja; Brockmann, Klaus J; Stroh, Fred; Benter, Thorsten

    2014-01-01

    In this study a thermally sampling atmospheric pressure ionization mass spectrometer is described and characterized. The ion transfer stage offers the capability to sample cluster ions at thermal equilibrium and during this transfer fundamental processes possibly affecting the cluster distribution are also readily identified. Additionally, the transfer stage combines optional collision-induced dissociation (CID) analysis of the cluster composition with thermal equilibrium sampling of clusters. The performance of the setup is demonstrated with regard to the proton-bound water cluster system. The benefit of the studied processes is that they can help to improve future transfer stages and to understand cluster ion reactions in ion mobility tubes and high-pressure ion sources. In addition, the instrument allows for the identification of fragmentation and protonation reactions caused by CID. PMID:24517784

  17. Tailoring the electron dynamics and chemical kinetics in radio-frequency driven atmospheric pressure plasmas

    NASA Astrophysics Data System (ADS)

    Gans, Timo

    2015-09-01

    Radio-frequency atmospheric pressure plasmas are versatile and efficient sources for reactive species at ambient room temperature. The non-equilibrium chemical kinetics is initiated and determined by the electron dynamics. Due to the strongly collisional environment and associated short electron energy relaxation times the electron dynamics can be tailored using multi-frequency power coupling techniques, enabling separate control of key parameters like electron density and electron mean energy. Details of the chemical kinetics depend on the feedgas composition and desired application. Measurements and predictive simulations of key reactive species are equally challenging due to the strongly collisional environment and their multi-scale nature in space and time. The most promising approach is the exploitation of complementary advantages in direct measurements combined with specifically designed numerical simulations. The employed diagnostic techniques include picosecond laser spectroscopy, synchrotron VUV spectroscopy, IR absorption spectroscopy and nanosecond optical imaging spectroscopy. The presentation will focus on examples of He-O2-N2 mixtures for bio-medical applications and He/Ar-CO2 mixtures for CO2 conversion into value-added chemicals. This work has been supported by the UK EPSRC (EP/K018388/1 & EP/H003797/1).

  18. SFC-APLI-(TOF)MS: Hyphenation of Supercritical Fluid Chromatography to Atmospheric Pressure Laser Ionization Mass Spectrometry.

    PubMed

    Klink, Dennis; Schmitz, Oliver Johannes

    2016-01-01

    Atmospheric-pressure laser ionization mass spectrometry (APLI-MS) is a powerful method for the analysis of polycyclic aromatic hydrocarbon (PAH) molecules, which are ionized in a selective and highly sensitive way via resonance-enhanced multiphoton ionization. APLI was presented in 2005 and has been hyphenated successfully to chromatographic separation techniques like high performance liquid chromatography (HPLC) and gas chromatography (GC). In order to expand the portfolio of chromatographic couplings to APLI, a new hyphenation setup of APLI and supercritical-fluid chromatography (SFC) was constructed and aim of this work. Here, we demonstrate the first hyphenation of SFC and APLI in a simple designed way with respect to different optimization steps to ensure a sensitive analysis. The new setup permits qualitative and quantitative determination of native and also more polar PAH molecules. As a result of the altered ambient characteristics within the source enclosure, the quantification of 1-hydroxypyrene (1-HP) in human urine is possible without prior derivatization. The limit of detection for 1-HP by SFC-APLI-TOF(MS) was found to be 0.5 μg L(-1), which is lower than the 1-HP concentrations found in exposed persons. PMID:26633261

  19. Athabasca oil sands process water: characterization by atmospheric pressure photoionization and electrospray ionization fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

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

    2010-05-01

    The Athabasca oil sands in Canada are a less conventional source of oil which have seen rapid development. There are concerns about the environmental impact, with particular respect to components in oil sands process water which may enter the aquatic ecosystem. Naphthenic acids have been previously targeted for study, due to their implications in toxicity toward aquatic wildlife, but it is believed that other components, too, contribute toward the potential toxicity of the oil sands process water. When mass spectrometry is used, it is necessary to use instrumentation with a high resolving power and mass accuracy when studying complex mixtures, but the technique has previously been hindered by the range of compounds that have been accessible via common ionization techniques, such as electrospray ionization. The research described here applied Fourier transform ion cyclotron resonance mass spectrometry in conjunction with electrospray ionization and atmospheric pressure photoionization, in both positive-ion and negative-ion modes, to the characterization of oil sands process water for the first time. The results highlight the need for broader characterization when investigating toxic components within oil sands process water. PMID:20359201

  20. Plasma-spray ionization (PLASI): a multimodal atmospheric pressure ion source for liquid stream analysis.

    PubMed

    Kaylor, Adam; Dwivedi, Prabha; Pittman, Jennifer J; Monge, María Eugenia; Cheng, Guilong; Li, Shelly; Fernández, Facundo M

    2014-10-01

    A new ion generation method, named plasma-spray ionization (PLASI) for direct analysis of liquid streams, such as in continuous infusion experiments or liquid chromatography (LC), is reported. PLASI addresses many of the analytical limitations of electrospray ionization (ESI) and has potential for real time process stream analysis and reaction monitoring under atmospheric conditions in non-ESI friendly scenarios. In PLASI-mass spectrometry (MS), the liquid stream is pneumatically nebulized and partially charged at low voltages; the resultant aerosol is thus entrained with a gaseous plasma plume from a distal glow discharge prior to MS detection. PLASI-MS not only overcomes ESI-MS limitations but also generates simpler mass spectra with minimal adduct and cluster formation. PLASI utilizes the atomization capabilities of an ESI sprayer operated below the ESI threshold to generate gas-phase aerosols that are then ionized by the plasma stream. When operated at or above the ESI threshold, ionization by traditional ESI mechanisms is achieved. The multimodal nature of the technique enables readily switching between plasma and ESI operation. It is expected that PLASI will enable analyzing a wide range of analytes in complex matrices and less-restricted solvent systems, providing more flexibility than that achievable by ESI alone. PMID:25001384

  1. Surface Decontamination of Chemical Agent Surrogates Using an Atmospheric Pressure Air Flow Plasma Jet

    NASA Astrophysics Data System (ADS)

    Li, Zhanguo; Li, Ying; Cao, Peng; Zhao, Hongjie

    2013-07-01

    An atmospheric pressure dielectric barrier discharge (DBD) plasma jet generator using air flow as the feedstock gas was applied to decontaminate the chemical agent surrogates on the surface of aluminum, stainless steel or iron plate painted with alkyd or PVC. The experimental results of material decontamination show that the residual chemical agent on the material is lower than the permissible value of the National Military Standard of China. In order to test the corrosion effect of the plasma jet on different material surfaces in the decontamination process, corrosion tests for the materials of polymethyl methacrylate, neoprene, polyvinyl chloride (PVC), polyethylene (PE), phenolic resin, iron plate painted with alkyd, stainless steel, aluminum, etc. were carried out, and relevant parameters were examined, including etiolation index, chromatism, loss of gloss, corrosion form, etc. The results show that the plasma jet is slightly corrosive for part of the materials, but their performances are not affected. A portable calculator, computer display, mainboard, circuit board of radiogram, and a hygrometer could work normally after being treated by the plasma jet.

  2. A systematic study of atmospheric pressure chemical vapor deposition growth of large-area monolayer graphene†

    PubMed Central

    Liu, Lixin; Zhou, Hailong; Cheng, Rui; Chen, Yu; Lin, Yung-Chen; Qu, Yongquan; Bai, Jingwei; Ivanov, Ivan A.; Liu, Gang

    2012-01-01

    Graphene has attracted considerable interest as a potential material for future electronics. Although mechanical peel is known to produce high quality graphene flakes, practical applications require continuous graphene layers over a large area. The catalyst-assisted chemical vapor deposition (CVD) is a promising synthetic method to deliver wafer-sized graphene. Here we present a systematic study on the nucleation and growth of crystallized graphene domains in an atmospheric pressure chemical vapor deposition (APCVD) process. Parametric studies show that the mean size of the graphene domains increases with increasing growth temperature and CH4 partial pressure, while the density of domains decreases with increasing growth temperature and is independent of the CH4 partial pressure. Our studies show that nucleation of graphene domains on copper substrate is highly dependent on the initial annealing temperature. A two-step synthetic process with higher initial annealing temperature but lower growth temperature is developed to reduce domain density and achieve high quality full-surface coverage of monolayer graphene films. Electrical transport measurements demonstrate that the resulting graphene exhibits a high carrier mobility of up to 3000 cm2 V−1 s−1 at room temperature. PMID:25414547

  3. Atmospheric pressure femtosecond laser imaging mass spectrometry

    NASA Astrophysics Data System (ADS)

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

    2009-02-01

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

  4. Atmospheric pressure-thermal desorption (AP-TD)/electrospray ionization-mass spectrometry for the rapid analysis of Bacillus spores.

    PubMed

    Basile, Franco; Zhang, Shaofeng; Shin, Yong-Seung; Drolet, Barbara

    2010-04-01

    A technique is described where an atmospheric pressure-thermal desorption (AP-TD) device and electrospray ionization (ESI)-mass spectrometry (MS) are coupled and used for the rapid analysis of Bacillus subtilis spores in complex matrices. The resulting AP-TD/ESI-MS technique combines the generation of volatile compounds and/or pyrolysis products with soft-ionization MS detection. In the AP-TD/ESI-MS approach, an electrospray solvent plume was used as the ionization vehicle of thermally desorbed neutrals at atmospheric pressure prior to mass spectrometric analysis using a quadrupole ion trap mass spectrometer. The approach is quantitative with the volatile standard dimethyl methylphosphonate (DMMP) and with the use of an internal standard (diethyl methylphosphonate, DEMP). A linear response was obtained as tested in the 1-50 ppm range (R(2) = 0.991) with a standard error of the estimate of 0.193 (0.9% RSD, n = 5). Bacterial spores were detected by performing pyrolysis in situ methylation with the reagent tetramethylammonium hydroxide (TMAH) for the detection of the bacterial spore biomarker dipicolinic acid (DPA) as the dimethylated derivative (2Me-DPA). This approach allowed spore detection even in the presence of growth media in crude lyophilized samples. Repetitive analyses could be performed with a duty cycle of less than 5 min total analysis time (including sample loading, heating and data acquisition). This strategy proved successful over other direct ambient MS approaches like DESI-MS and AP-TD/ESI-MS without the in situ derivatization step to detect the dipicolinic acid biomarker from spores. A detection limit for the dimethylated DPA biomarker was estimated at 1 ppm (equivalent to 0.01 mug of DPA deposited in the thermal desorption tube), which corresponded to a calculated detection limit of 10(5) spores deposited or 0.1% by weight spore composition in solid samples (assuming a 1 mg sample size). The AP-TD/ESI source used in conjunction with the in situ

  5. Laser ablation electrospray ionization for atmospheric pressure, in vivo, and imaging mass spectrometry.

    PubMed

    Nemes, Peter; Vertes, Akos

    2007-11-01

    Mass spectrometric analysis of biomolecules under ambient conditions promises to enable the in vivo investigation of diverse biochemical changes in organisms with high specificity. Here we report on a novel combination of infrared laser ablation with electrospray ionization (LAESI) as an ambient ion source for mass spectrometry. As a result of the interactions between the ablation plume and the spray, LAESI accomplishes electrospray-like ionization. Without any sample preparation or pretreatment, this technique was capable of detecting a variety of molecular classes and size ranges (up to 66 kDa) with a detection limit of 8 and 25 fmol for verapamil and reserpine, respectively, and quantitation capabilities with a four-decade dynamic range. We demonstrated the utility of LAESI in a broad variety of applications ranging from plant biology to clinical analysis. Proteins, lipids, and metabolites were identified, and antihistamine excretion was followed via the direct analysis of bodily fluids (urine, blood, and serum). We also performed in vivo spatial profiling (on leaf, stem, and root) of metabolites in a French marigold (Tagetes patula) seedling. PMID:17900146

  6. Combinatorial atmospheric pressure chemical vapor deposition (cAPCVD): a route to functional property optimization.

    PubMed

    Kafizas, Andreas; Parkin, Ivan P

    2011-12-21

    We demonstrate how combinatorial atmospheric pressure chemical vapor deposition (cAPCVD) can be used as a synthetic tool for rapidly optimizing the functional properties of thin-films, by analyzing the self-cleaning properties of tungsten doped anatase as an example. By introducing reagents at separate points inside the reactor, a tungsten/titanium compositional gradient was formed and a diverse range of film growth conditions were obtained. By partially mixing the metal sources, a combinatorial film with a compositional profile that varied primarily in the lateral plane was synthesized. A combinatorial thin-film of anatase TiO(2) doped with an array of tungsten levels as a solid solution ranging from 0.38-13.8 W/Ti atom % was formed on a single glass substrate. The compositional-functional relationships were understood through comprehensively analyzing combinatorial phase space, with 200 positions investigated by high-throughput methods in this study. Physical and functional properties, and their compositional dependencies, were intercorrelated. It was found that increases in photocatalytic activity and conductivity were most highly dependent on film crystallinity within the 0.38-13.8 atom % W/Ti doping regime. However, enhancements in photoinduced surface wetting were primarily dependent on increases in preferred growth in the (211) crystal plane. PMID:22050427

  7. Atmospheric Pressure Spray Chemical Vapor Deposited CuInS2 Thin Films for Photovoltaic Applications

    NASA Technical Reports Server (NTRS)

    Harris, J. D.; Raffaelle, R. P.; Banger, K. K.; Smith, M. A.; Scheiman, D. A.; Hepp, A. F.

    2002-01-01

    Solar cells have been prepared using atmospheric pressure spray chemical vapor deposited CuInS2 absorbers. The CuInS2 films were deposited at 390 C using the single source precursor (PPh3)2CuIn(SEt)4 in an argon atmosphere. The absorber ranges in thickness from 0.75 - 1.0 micrometers, and exhibits a crystallographic gradient, with the leading edge having a (220) preferred orientation and the trailing edge having a (112) orientation. Schottky diodes prepared by thermal evaporation of aluminum contacts on to the CuInS2 yielded diodes for films that were annealed at 600 C. Solar cells were prepared using annealed films and had the (top down) composition of Al/ZnO/CdS/CuInS2/Mo/Glass. The Jsc, Voc, FF and (eta) were 6.46 mA per square centimeter, 307 mV, 24% and 0.35%, respectively for the best small area cells under simulated AM0 illumination.

  8. Inactivation of virus in solution by cold atmospheric pressure plasma: identification of chemical inactivation pathways

    NASA Astrophysics Data System (ADS)

    Aboubakr, Hamada A.; Gangal, Urvashi; Youssef, Mohammed M.; Goyal, Sagar M.; Bruggeman, Peter J.

    2016-05-01

    Cold atmospheric pressure plasma (CAP) inactivates bacteria and virus through in situ production of reactive oxygen and nitrogen species (RONS). While the bactericidal and virucidal efficiency of plasmas is well established, there is limited knowledge about the chemistry leading to the pathogen inactivation. This article describes a chemical analysis of the CAP reactive chemistry involved in the inactivation of feline calicivirus. We used a remote radio frequency CAP produced in varying gas mixtures leading to different plasma-induced chemistries. A study of the effects of selected scavengers complemented with positive control measurements of relevant RONS reveal two distinctive pathways based on singlet oxygen and peroxynitrous acid. The first mechanism is favored in the presence of oxygen and the second in the presence of air when a significant pH reduction is induced in the solution by the plasma. Additionally, smaller effects of the H2O2, O3 and \\text{NO}2- produced were also found. Identification of singlet oxygen-mediated 2-imidazolone/2-oxo-His (His  +14 Da)—an oxidative modification of His 262 comprising the capsid protein of feline calicivirus links the plasma induced singlet oxygen chemistry to viral inactivation.

  9. Chain Assemblies from Nanoparticles Synthesized by Atmospheric Pressure Plasma Enhanced Chemical Vapor Deposition: The Computational View.

    PubMed

    Mishin, Maxim V; Zamotin, Kirill Y; Protopopova, Vera S; Alexandrov, Sergey E

    2015-12-01

    This article refers to the computational study of nanoparticle self-organization on the solid-state substrate surface with consideration of the experimental results, when nanoparticles were synthesised during atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD). The experimental study of silicon dioxide nanoparticle synthesis by AP-PECVD demonstrated that all deposit volume consists of tangled chains of nanoparticles. In certain cases, micron-sized fractals are formed from tangled chains due to deposit rearrangement. This work is focused on the study of tangled chain formation only. In order to reveal their formation mechanism, a physico-mathematical model was developed. The suggested model was based on the motion equation solution for charged and neutral nanoparticles in the potential fields with the use of the empirical interaction potentials. In addition, the computational simulation was carried out based on the suggested model. As a result, the influence of such experimental parameters as deposition duration, particle charge, gas flow velocity, and angle of gas flow was found. It was demonstrated that electrical charges carried by nanoparticles from the discharge area are not responsible for the formation of tangled chains from nanoparticles, whereas nanoparticle kinetic energy plays a crucial role in deposit morphology and density. The computational results were consistent with experimental results. PMID:26682441

  10. Diamond synthesis at atmospheric pressure by microwave capillary plasma chemical vapor deposition

    SciTech Connect

    Hemawan, Kadek W.; Gou, Huiyang; Hemley, Russell J.

    2015-11-02

    Polycrystalline diamond has been synthesized on silicon substrates at atmospheric pressure, using a microwave capillary plasma chemical vapor deposition technique. The CH{sub 4}/Ar plasma was generated inside of quartz capillary tubes using 2.45 GHz microwave excitation without adding H{sub 2} into the deposition gas chemistry. Electronically excited species of CN, C{sub 2}, Ar, N{sub 2}, CH, H{sub β}, and H{sub α} were observed in the emission spectra. Raman measurements of deposited material indicate the formation of well-crystallized diamond, as evidenced by the sharp T{sub 2g} phonon at 1333 cm{sup −1} peak relative to the Raman features of graphitic carbon. Field emission scanning electron microscopy images reveal that, depending on the growth conditions, the carbon microstructures of grown films exhibit “coral” and “cauliflower-like” morphologies or well-facetted diamond crystals with grain sizes ranging from 100 nm to 10 μm.

  11. Threefold atmospheric-pressure annealing for suppressing graphene nucleation on copper in chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Suzuki, Seiya; Nagamori, Takashi; Matsuoka, Yuki; Yoshimura, Masamichi

    2014-09-01

    Chemical vapor deposition (CVD) is a promising method of producing a large single-crystal graphene on a catalyst, especially on copper (Cu), and a further increase in domain size is desirable for electro/optic applications. Here, we report on threefold atmospheric-pressure (ATM) annealing for suppressing graphene nucleation in atmospheric CVD. Threefold ATM annealing formed a step and terrace surface of the underlying Cu, in contrast to ATM annealing. Atomic force microscopy and Auger electron mapping revealed that Si-containing particles existed on threefold-ATM- and ATM-annealed surfaces; particles on Cu had a lower density after threefold ATM annealing than after ATM annealing. The formation of a step and terrace surface and the lower density of particles following the threefold ATM annealing would play a role in reducing graphene nucleation. By combining threefold ATM annealing and electropolishing of Cu, the nucleation of graphene was effectively suppressed, and a submillimeter-sized hexagonal single-crystal graphene was successfully obtained.

  12. Atmospheric-Pressure Chemical Vapor Deposition of Iron Pyrite Thin Films

    SciTech Connect

    Berry, Nicholas; Cheng, Ming; Perkins, Craig L.; Limpinsel, Moritz; Hemminger, John C.; Law, Matt

    2012-10-23

    Iron pyrite (cubic FeS{sub 2}) is a promising candidate absorber material for earth-abundant thin-film solar cells. In this report, single-phase, large-grain, and uniform polycrystalline pyrite thin films are fabricated on glass and molybdenum-coated glass substrates by atmospheric-pressure chemical vapor deposition (AP-CVD) using the reaction of iron(III) acetylacetonate and tert-butyl disulfide in argon at 300 C, followed by sulfur annealing at 500--550 C to convert marcasite impurities to pyrite. The pyrite-marcasite phase composition depends strongly on the concentration of sodium in the growth substrate and the sulfur partial pressure during annealing. Phase and elemental composition of the films are characterized by X-ray diffraction, Raman spectroscopy, Auger electron spectroscopy, secondary ion mass spectrometry, Rutherford backscattering spectrometry, and X-ray photoelectron spectroscopy. The in-plane electrical properties are surprisingly insensitive to phase and elemental impurities, with all films showing p-type, thermally activated transport with a small activation energy ({approx}30 meV), a room- temperature resistivity of {approx}1 {Omega} cm, and low mobility. These ubiquitous electrical properties may result from robust surface effects. These CVD pyrite thin films are well suited to fundamental electrical studies and the fabrication of pyrite photovoltaic device stacks.

  13. Analysis of psychoactive cathinones and tryptamines by electrospray ionization atmospheric pressure ion mobility time-of-flight mass spectrometry.

    PubMed

    Kanu, A Bakarr; Brandt, Simon D; Williams, Mike D; Zhang, Nancy; Hill, Herbert H

    2013-09-17

    The ability to use positive ion monitoring mode with an atmospheric pressure ion mobility time-of-flight mass spectrometer (APIM(tof)MS) to detect psychoactive cathinones and tryptamines from aqueous phase samples was evaluated. The study used a traditional electrospray ionization (ESI) source for sample introduction and ionization. A total of four cathinones (mephedrone, butylone, 4-Me-PPP, and 4-MEC) and five tryptamines (5-EtO-DPT, 5-EtO-DALT, 5-EtO-MIPT, 5-EtO-ALCHT, and 5-EtO-2MALET) were investigated, and we report on parent ions, collision induced dissociation (CID) fragment ions, reduced mobility (Ko), mass flight times, and detection limits obtained from a single instrument run for the psychoactive substances. Detection limits reported ranged from 3 to 11 μM concentration for the compounds studied. This detection limit range corresponded to 1-5 ng of material needed for improved detection on the instrument. This article demonstrates that it was possible to use a single instrument platform for the separation, detection, and identification of cathinones and tryptamines in less than 1 min. The application holds great promise for detecting and identifying a new class of drugs often referred to as "bath salts" or "legal highs" distributed over the Internet. PMID:23875808

  14. Off-axis chemical crosstalk in an atmospheric pressure microplasma jet array

    NASA Astrophysics Data System (ADS)

    Sun, P. P.; Chen, H. L.; Park, S.-J.; Eden, J. G.; Liu, D. X.; Kong, M. G.

    2015-10-01

    Developing arrays of parallel microplasma jets is an attractive route to scaling the area available for the treatment of surfaces with low temperature plasma. Increasing the packing density of the arrays may lead to electrical and gas kinetic jet-jet interactions, but previous work has focused almost exclusively on electrostatic coupling between the jets. Chemical interactions (‘crosstalk’) have received considerably less attention. We report here the results of an investigation of chemical crosstalk in 4  ×  4 arrays of microplasma jets, produced in flowing helium at atmospheric pressure. Oxidation damage to an Escherichia coli lawn serves as a diagnostic of the spatial distribution of molecular radicals and other reactive plasma species, produced at the plasma jet/ambient background interface or between the jets, and incident on the surface. Spatial maps of bacterial inactivation by the microplasma jet array for 20 s show the destruction of E. coli at distances as large as 2.7 jet diameter from the nearest plasma perimeter, compared to typically less than 0.5 jet diameter in the single jet case. Extending to 30 s of plasma exposure leads to destruction of the entire bacterial sample. This ‘action at a distance’ effect, the production of long-lived species such as O, O2(a1Δg) and O3 that are responsible for bacterial deactivation, peaks along a line bisecting columns and rows of plasma jets. The data illustrate the synergistic effect of adjacent jets on off-axis formation of reactive species, and show that the chemical and biological impact of an array cannot be inferred from the plasma chemistry of a single jet.

  15. Atmospheric pressure ionization of chlorinated ethanes in ion mobility spectrometry and mass spectrometry

    SciTech Connect

    Ewing, Robert G.; Atkinson, David A.; Benson, Michael T.

    2015-05-16

    This study investigates the APCI mechanisms associated with chlorinated ethanes in an attempt to define conditions under which unique pseudo-molecular adducts, in addition to chloride ion, can be produced for analytical measurements using IMS and MS. The ionization chemistry of chlorinated compounds typically leads to the detection of only the halide ions. Using molecular modeling, which provides insights into the ion formation and relative binding energies, predictions for the formation of pseudo-molecular adducts are postulated. Predicted structures of the chloride ion with multiple hydrogens on the ethane backbone was supported by the observation of specific pseudo-molecular adducts in IMS and MS spectra. With the proper instrumental conditions, such as short reaction times and low temp.

  16. Optimization and application of atmospheric pressure chemical and photoionization hydrogen-deuterium exchange mass spectrometry for speciation of oxygen-containing compounds.

    PubMed

    Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Jin, Jang Mi; Yim, Un Hyuk; Shim, Won Joon; Kim, Young Hwan; Kim, Sunghwan

    2016-05-01

    This paper presents a detailed investigation of the feasibility of optimized positive and negative atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and atmospheric pressure photoionization (APPI) MS coupled to hydrogen-deuterium exchange (HDX) for structural assignment of diverse oxygen-containing compounds. The important parameters for optimization of HDX MS were characterized. The optimized techniques employed in the positive and negative modes showed satisfactory HDX product ions for the model compounds when dichloromethane and toluene were employed as a co-solvent in APCI- and APPI-HDX, respectively. The evaluation of the mass spectra obtained from 38 oxygen-containing compounds demonstrated that the extent of the HDX of the ions was structure-dependent. The combination of information provided by different ionization techniques could be used for better speciation of oxygen-containing compounds. For example, (+) APPI-HDX is sensitive to compounds with alcohol, ketone, or aldehyde substituents, while (-) APPI-HDX is sensitive to compounds with carboxylic functional groups. In addition, the compounds with alcohol can be distinguished from other compounds by the presence of exchanged peaks. The combined information was applied to study chemical compositions of degraded oils. The HDX pattern, double bond equivalent (DBE) distribution, and previously reported oxidation products were combined to predict structures of the compounds produced from oxidation of oil. Overall, this study shows that APCI- and APPI-HDX MS are useful experimental techniques that can be applied for the structural analysis of oxygen-containing compounds. PMID:26898203

  17. Low temperature atmospheric pressure chemical vapor deposition of group 14 oxide films

    SciTech Connect

    Hoffman, D.M.; Atagi, L.M. |; Chu, Wei-Kan; Liu, Jia-Rui; Zheng, Zongshuang; Rubiano, R.R.; Springer, R.W.; Smith, D.C.

    1994-06-01

    Depositions of high quality SiO{sub 2} and SnO{sub 2} films from the reaction of homoleptic amido precursors M(NMe{sub 2})4 (M = Si,Sn) and oxygen were carried out in an atmospheric pressure chemical vapor deposition r. The films were deposited on silicon, glass and quartz substrates at temperatures of 250 to 450C. The silicon dioxide films are stoichiometric (O/Si = 2.0) with less than 0.2 atom % C and 0.3 atom % N and have hydrogen contents of 9 {plus_minus} 5 atom %. They are deposited with growth rates from 380 to 900 {angstrom}/min. The refractive indexes of the SiO{sub 2} films are 1.46, and infrared spectra show a possible Si-OH peak at 950 cm{sup {minus}1}. X-Ray diffraction studies reveal that the SiO{sub 2} film deposited at 350C is amorphous. The tin oxide films are stoichiometric (O/Sn = 2.0) and contain less than 0.8 atom % carbon, and 0.3 atom % N. No hydrogen was detected by elastic recoil spectroscopy. The band gap for the SnO{sub 2} films, as estimated from transmission spectra, is 3.9 eV. The resistivities of the tin oxide films are in the range 10{sup {minus}2} to 10{sup {minus}3} {Omega}cm and do not vary significantly with deposition temperature. The tin oxide film deposited at 350C is cassitterite with some (101) orientation.

  18. Collision-induced dissociation analysis of negative atmospheric ion adducts in atmospheric pressure corona discharge ionization mass spectrometry.

    PubMed

    Sekimoto, Kanako; Takayama, Mitsuo

    2013-05-01

    Collision-induced dissociation (CID) experiments were performed on atmospheric ion adducts [M + R](-) formed between various types of organic compounds M and atmospheric negative ions R(-) [such as O2(-), HCO3(-), COO(-)(COOH), NO2(-), NO3(-), and NO3(-)(HNO3)] in negative-ion mode atmospheric pressure corona discharge ionization (APCDI) mass spectrometry. All of the [M + R](-) adducts were fragmented to form deprotonated analytes [M - H](-) and/or atmospheric ions R(-), whose intensities in the CID spectra were dependent on the proton affinities of the [M - H](-) and R(-) fragments. Precursor ions [M + R](-) for which R(-) have higher proton affinities than [M - H](-) formed [M - H](-) as the dominant product. Furthermore, the CID of the adducts with HCO3(-) and NO3(-)(HNO3) led to other product ions such as [M + HO](-) and NO3(-), respectively. The fragmentation behavior of [M + R](-) for each R(-) observed was independent of analyte type (e.g., whether the analyte was aliphatic or aromatic, or possessed certain functional groups). PMID:23479312

  19. Desorption/ionization of biomolecules from aqueous solutions at atmospheric pressure using an infrared laser at 3 microm.

    PubMed

    Laiko, Victor V; Taranenko, Nelli I; Berkout, Vadym D; Yakshin, Mikhail A; Prasad, Coorg R; Lee, H Sang; Doroshenko, Vladimir M

    2002-04-01

    A new atmospheric pressure (AP) infrared (IR) matrix-assisted laser desorption/ionization (MALDI) ion source was developed and interfaced with a Thermo Finnigan LCQ ion trap mass spectrometer. The source utilized a miniature all-solid-state optical parametric oscillator (OPO)-based IR laser system tunable in the lambda = 1.5-4 microm spectral range and a nitrogen ultraviolet (UV) laser (lambda = 337 nm) for use in comparative studies. The system demonstrated comparable performance at 3 microm and 337 nm wavelengths if UV matrices were used. However, AP IR-MALDI using a 3 microm wavelength showed good performance with a much broader choice of matrices including glycerol and liquid water. AP IR-MALDI mass spectra of peptides in the mass range up to 2000 Da were obtained directly from aqueous solutions at atmospheric conditions for the first time. A potential use of the new AP IR-MALDI ion source includes direct MS analysis of biological cells and tissues in a normal atmospheric environment as well as on-line coupling of mass spectrometers with liquid separation techniques. PMID:11951973

  20. Capillary electrochromatography-atmospheric pressure ionization mass spectrometry of pesticides using a surfactant-bound monolithic column

    PubMed Central

    Gu, Congying; Shamsi, Shahab A.

    2011-01-01

    A surfactant bound poly (11-acrylaminoundecanoic acid-ethylene dimethacrylate) (AAUA-EDMA) monolithic column was simply prepared by in-situ co-polymerization of AAUA and EDMA with 1-propanol, 1,4-butanediol and water as porogens in 100 µm id fused silica capillary in one step. This column was used in capillary electrochromatography (CEC)-atmospheric pressure photoionization (APPI)-mass spectrometry system for separation and detection of N-methylcarbamates (NMCs) pesticides. Numerous parameters are optimized for CEC-APPI-MS. After evaluation of the mobile phase composition, sheath liquid composition and the monolithic capillary outlet position, a fractional factorial design (FFD) was selected as a screening procedure to identify factors of ionization source parameters, such as sheath liquid flow rate, drying gas flow rate, drying gas temperature, nebulizing gas pressure, vaporizer temperature, and capillary voltage, which significantly influence APPI-MS sensitivity. A face-centered central composite design (CCD) was further utilized to optimize the most significant parameters and predict the best sensitivity. Under optimized conditions signal-to-noise ratios (S/N) around 78 were achieved for an injection of 100 ng/mL of each pesticide. Finally, this CEC-APPI-MS method was successfully applied to the analysis of nine NMCs in spiked apple juice sample after solid phase extraction with recoveries in the range of 65 to 109%. PMID:20349511

  1. On-line coating of glass with tin oxide by atmospheric pressure chemical vapor deposition.

    SciTech Connect

    Allendorf, Mark D.; Sopko, J.F. (PPF Industries, Pittsburgh, PA); Houf, William G.; Chae, Yong Kee; McDaniel, Anthony H.; Li, M. (PPF Industries, Pittsburgh, PA); McCamy, J.W.

    2006-11-01

    Atmospheric pressure chemical vapor deposition (APCVD) of tin oxide is a very important manufacturing technique used in the production of low-emissivity glass. It is also the primary method used to provide wear-resistant coatings on glass containers. The complexity of these systems, which involve chemical reactions in both the gas phase and on the deposition surface, as well as complex fluid dynamics, makes process optimization and design of new coating reactors a very difficult task. In 2001 the U.S. Dept. of Energy Industrial Technologies Program Glass Industry of the Future Team funded a project to address the need for more accurate data concerning the tin oxide APCVD process. This report presents a case study of on-line APCVD using organometallic precursors, which are the primary reactants used in industrial coating processes. Research staff at Sandia National Laboratories in Livermore, CA, and the PPG Industries Glass Technology Center in Pittsburgh, PA collaborated to produce this work. In this report, we describe a detailed investigation of the factors controlling the growth of tin oxide films. The report begins with a discussion of the basic elements of the deposition chemistry, including gas-phase thermochemistry of tin species and mechanisms of chemical reactions involved in the decomposition of tin precursors. These results provide the basis for experimental investigations in which tin oxide growth rates were measured as a function of all major process variables. The experiments focused on growth from monobutyltintrichloride (MBTC) since this is one of the two primary precursors used industrially. There are almost no reliable growth-rate data available for this precursor. Robust models describing the growth rate as a function of these variables are derived from modeling of these data. Finally, the results are used to conduct computational fluid dynamic simulations of both pilot- and full-scale coating reactors. As a result, general conclusions are

  2. Laserspray ionization, a new method for protein analysis directly from tissue at atmospheric pressure with ultrahigh mass resolution and electron transfer dissociation.

    PubMed

    Inutan, Ellen D; Richards, Alicia L; Wager-Miller, James; Mackie, Ken; McEwen, Charles N; Trimpin, Sarah

    2011-02-01

    Laserspray ionization (LSI) mass spectrometry (MS) allows, for the first time, the analysis of proteins directly from tissue using high performance atmospheric pressure ionization mass spectrometers. Several abundant and numerous lower abundant protein ions with molecular masses up to ∼20,000 Da were detected as highly charged ions from delipified mouse brain tissue mounted on a common microscope slide and coated with 2,5-dihydroxyacetophenone as matrix. The ability of LSI to produce multiply charged ions by laser ablation at atmospheric pressure allowed protein analysis at 100,000 mass resolution on an Orbitrap Exactive Fourier transform mass spectrometer. A single acquisition was sufficient to identify the myelin basic protein N-terminal fragment directly from tissue using electron transfer dissociation on a linear trap quadrupole (LTQ) Velos. The high mass resolution and mass accuracy, also obtained with a single acquisition, are useful in determining protein molecular weights and from the electron transfer dissociation data in confirming database-generated sequences. Furthermore, microscopy images of the ablated areas show matrix ablation of ∼15 μm-diameter spots in this study. The results suggest that LSI-MS at atmospheric pressure potentially combines speed of analysis and imaging capability common to matrix-assisted laser desorption/ionization and soft ionization, multiple charging, improved fragmentation, and cross-section analysis common to electrospray ionization. PMID:20855542

  3. Distinguishing N-oxide and hydroxyl compounds: impact of heated capillary/heated ion transfer tube in inducing atmospheric pressure ionization source decompositions.

    PubMed

    Peiris, Dilrukshi M; Lam, Wing; Michael, Steven; Ramanathan, Ragu

    2004-06-01

    In the pharmaceutical industry, a higher attrition rate during the drug discovery process means a lower drug failure rate in the later stages. This translates into shorter drug development time and reduced cost for bringing a drug to market. Over the past few years, analytical strategies based on liquid chromatography/mass spectrometry (LC/MS) have gone through revolutionary changes and presently accommodate most of the needs of the pharmaceutical industry. Among these LC/MS techniques, collision induced dissociation (CID) or tandem mass spectrometry (MS/MS and MS(n)) techniques have been widely used to identify unknown compounds and characterize metabolites. MS/MS methods are generally ineffective for distinguishing isomeric compounds such as metabolites involving oxygenation of carbon or nitrogen atoms. Most recently, atmospheric pressure ionization (API) source decomposition methods have been shown to aid in the mass spectral distinction of isomeric oxygenated (N-oxide vs hydroxyl) products/metabolites. In previous studies, experiments were conducted using mass spectrometers equipped with a heated capillary interface between the mass analyzer and the ionization source. In the present study, we investigated the impact of the length of a heated capillary or heated ion transfer tube (a newer version of the heated capillary designed for accommodating orthogonal API source design) in inducing for-API source deoxygenation that allows the distinction of N-oxide from hydroxyl compounds. 8-Hydroxyquinoline (HO-Q), quinoline-N-oxide (Q-NO) and 8-hydroxyquinoline-N-oxide (HO-Q-NO) were used as model compounds on three different mass spectrometers (LCQ Deca, LCQ Advantage and TSQ Quantum). Irrespective of heated capillary or ion transfer tube length, N-oxides from this class of compounds underwent predominantly deoxygenation decomposition under atmospheric pressure chemical ionization conditions and the abundance of the diagnostic [M + H - O](+) ions increased with

  4. Screening of lake sediments for emerging contaminants by liquid chromatography atmospheric pressure photoionization and electrospray ionization coupled to high resolution mass spectrometry.

    PubMed

    Chiaia-Hernandez, Aurea C; Krauss, Martin; Hollender, Juliane

    2013-01-15

    We developed a multiresidue method for the target and suspect screening of more than 180 pharmaceuticals, personal care products, pesticides, biocides, additives, corrosion inhibitors, musk fragrances, UV light stabilizers, and industrial chemicals in sediments. Sediment samples were freeze-dried, extracted by pressurized liquid extraction, and cleaned up by liquid-liquid partitioning. The quantification and identification of target compounds with a broad range of physicochemical properties (log K(ow) 0-12) was carried out by liquid chromatography followed by electrospray ionization (ESI) and atmospheric pressure photoionization (APPI) coupled to high resolution Orbitrap mass spectrometry (HRMS/MS). The overall method average recoveries and precision are 103% and 9% (RSD), respectively. The method detection limits range from 0.010 to 4 ng/g(dw), while limits of quantification range from 0.030 to 14 ng/g(dw). The use of APPI as an alternative ionization source helped to distinguish two isomeric musk fragrances by means of different ionization behavior. The method was demonstrated on sediment cores from Lake Greifensee located in northeastern Switzerland. The results show that biocides, musk fragrances, and other personal care products were the most frequently detected compounds with concentrations ranging from pg/g(dw) to ng/g(dw), whereas none of the targeted pharmaceuticals were found. The concentrations of many urban contaminants originating from wastewater correlate with the highest phosphorus input into the lake as a proxy for treatment efficiency. HRMS enabled a retrospective analysis of the full-scan data acquisition allowing the detection of suspected compounds like quaternary ammonium surfactants, the biocide triclocarban, and the tentative identification of further compounds without reference standards, among others transformation products of triclosan and triclocarban. PMID:23215447

  5. Liquid chromatography coupled to different atmospheric pressure ionization sources-quadrupole-time-of-flight mass spectrometry and post-column addition of metal salt solutions as a powerful tool for the metabolic profiling of Fusarium oxysporum.

    PubMed

    Cirigliano, Adriana M; Rodriguez, M Alejandra; Gagliano, M Laura; Bertinetti, Brenda V; Godeas, Alicia M; Cabrera, Gabriela M

    2016-03-25

    Fusarium oxysporum L11 is a non-pathogenic soil-borne fungal strain that yielded an extract that showed antifungal activity against phytopathogens. In this study, reversed-phase high-performance liquid chromatography (RP-HPLC) coupled to different atmospheric pressure ionization sources-quadrupole-time-of-flight mass spectrometry (API-QTOF-MS) was applied for the comprehensive profiling of the metabolites from the extract. The employed sources were electrospray (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI). Post-column addition of metal solutions of Ca, Cu and Zn(II) was also tested using ESI. A total of 137 compounds were identified or tentatively identified by matching their accurate mass signals, suggested molecular formulae and MS/MS analysis with previously reported data. Some compounds were isolated and identified by NMR. The extract was rich in cyclic peptides like cyclosporins, diketopiperazines and sansalvamides, most of which were new, and are reported here for the first time. The use of post-column addition of metals resulted in a useful strategy for the discrimination of compound classes since specific adducts were observed for the different compound families. This technique also allowed the screening for compounds with metal binding properties. Thus, the applied methodology is a useful choice for the metabolic profiling of extracts and also for the selection of metabolites with potential biological activities related to interactions with metal ions. PMID:26655791

  6. Synthesis of multi-layer graphene films on copper tape by atmospheric pressure chemical vapor deposition method

    NASA Astrophysics Data System (ADS)

    Nguyen, Van Tu; Doan Le, Huu; Chuc Nguyen, Van; Thanh Tam Ngo, Thi; Quang Le, Dinh; Nghia Nguyen, Xuan; Phan, Ngoc Minh

    2013-09-01

    Graphene films were successfully synthesized by atmospheric pressure chemical vapor deposition (APCVD) method. Methane (CH4) gas and copper (Cu) tapes were used as a carbon source and a catalyst, respectively. The CVD temperature and time were in the range of 800-1000 °C and 10 s to 45 min, respectively. The role of the CVD temperature and time on the growth of graphene films was investigated in detail via scanning electron microscopy (SEM) and Raman spectroscopy techniques. The results of SEM images and Raman spectra show that the quality of the graphene films was improved with increasing of CVD temperature due to the increase of catalytic activity.

  7. Three-dimensional modelling of horizontal chemical vapor deposition. I - MOCVD at atmospheric pressure

    NASA Technical Reports Server (NTRS)

    Ouazzani, Jalil; Rosenberger, Franz

    1990-01-01

    A systematic numerical study of the MOCVD of GaAs from trimethylgallium and arsine in hydrogen or nitrogen carrier gas at atmospheric pressure is reported. Three-dimensional effects are explored for CVD reactors with large and small cross-sectional aspect ratios, and the effects on growth rate uniformity of tilting the susceptor are investigated for various input flow rates. It is found that, for light carrier gases, thermal diffusion must be included in the model. Buoyancy-driven three-dimensional flow effects can greatly influence the growth rate distribution through the reactor. The importance of the proper design of the lateral thermal boundary conditions for obtaining layers of uniform thickness is emphasized.

  8. In situ identification of organic components of ink used in books from the 1900s by atmospheric pressure matrix assisted laser desorption ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Giurato, Laura; Candura, Andrea; Grasso, Giuseppe; Spoto, Giuseppe

    2009-11-01

    This paper describes the use of atmospheric pressure/matrix assisted laser desorption ionization-mass spectrometry (AP/MALDI-MS) as a spatially resolved analytical technique for the study of organic components of inks used to print coloured parts of ancient books. The possibility to operate at atmospheric pressure makes MALDI-MS a new in situ micro-destructive diagnostic tool suitable for analysing samples in air, simplifying the investigation of the organic components of artistic and archaeological objects. In this work, several organic dyes and pigments were identified in situ by analysing different coloured areas of books printed in the years 1911 and 1920. The detected colouring materials, which were available since the 1890s, were often identified as a mixture, confirming the typical procedures used in the lithographic printing processes. The matrix deposition and the laser desorption process did not cause visible alteration of the sample surface.

  9. Regulated In Situ Generation of Molecular Ions or Protonated Molecules under Atmospheric-Pressure Helium-Plasma-Ionization Mass Spectrometric Conditions

    NASA Astrophysics Data System (ADS)

    Gangam, Rekha; Pavlov, Julius; Attygalle, Athula B.

    2015-07-01

    In an enclosed atmospheric-pressure helium-plasma ionization (HePI) source engulfed with dehumidified ambient gases, molecular cations are generated from compounds such as toluene, bromobenzene, and iodobenzene. Evidently, the ionization is effected by a direct Penning mechanism attributable to interactions of the gas-phase analyte with metastable helium atoms. It is widely known that secondary ions generated from ambient gases also play an important role in the overall ionization process. For example, when the ambient gases bear even traces of moisture, the analytes are ionized by proton transfer reactions with gaseous H3O+. In this study, we demonstrate how a controlled variation of experimental conditions can manipulate the abundance of molecular ions and protonated molecules in a HePI source.

  10. Atmospheric pressure plasma chemical vapor deposition reactor for 100 mm wafers, optimized for minimum contamination at low gas flow rates

    NASA Astrophysics Data System (ADS)

    Anand, Venu; Nair, Aswathi R.; Shivashankar, S. A.; Mohan Rao, G.

    2015-08-01

    Gas discharge plasmas used for thinfilm deposition by plasma-enhanced chemical vapor deposition (PECVD) must be devoid of contaminants, like dust or active species which disturb the intended chemical reaction. In atmospheric pressure plasma systems employing an inert gas, the main source of such contamination is the residual air inside the system. To enable the construction of an atmospheric pressure plasma (APP) system with minimal contamination, we have carried out fluid dynamic simulation of the APP chamber into which an inert gas is injected at different mass flow rates. On the basis of the simulation results, we have designed and built a simple, scaled APP system, which is capable of holding a 100 mm substrate wafer, so that the presence of air (contamination) in the APP chamber is minimized with as low a flow rate of argon as possible. This is examined systematically by examining optical emission from the plasma as a function of inert gas flow rate. It is found that optical emission from the plasma shows the presence of atmospheric air, if the inlet argon flow rate is lowered below 300 sccm. That there is minimal contamination of the APP reactor built here, was verified by conducting an atmospheric pressure PECVD process under acetylene flow, combined with argon flow at 100 sccm and 500 sccm. The deposition of a polymer coating is confirmed by infrared spectroscopy. X-ray photoelectron spectroscopy shows that the polymer coating contains only 5% of oxygen, which is comparable to the oxygen content in polymer deposits obtained in low-pressure PECVD systems.

  11. Very narrow SiGe/Si quantum wells deposited by low-temperature atmospheric pressure chemical vapor deposition

    SciTech Connect

    Gruetzmacher, D.A.; Sedgwick, T.O.; Northrop, G.A.

    1993-05-01

    The optical, structural, and electrical properties of very narrow SiGe quantum wells grown by {open_quotes}ultra-clean{close_quotes} atmospheric pressure chemical vapor deposition (APCVD) are investigated. X-ray reflectivity data reveal abrupt interfaces with a root-mean-square roughness of not more than 0.2 nm. For the first time narrow (4.3 meV) excitonic photoluminescence (PL) spectra were obtained from APCVD grown samples containing SiGe wells with 12.5% to 32.5% Ge. For the narrowest wells PL doublets are observed which are attributed to atomic steps at the SiGe/Si interfaces. The Pl and x-ray diffractometry data show that process deposition control for well and barrier width is within the monolayer range. Resonant tunneling diodes fabricated with 2.5-mm-wide Si{sub 0.75}Ge{sub 0.25} wells show world record peak to valley ratios of 4.2. Magneto-transport measurements performed at high magnetic fields of two-dimensional hole gases exhibit pronounced Hall plateaus and well-defined Shubnikov de Hass oscillations, indicating high material quality. The results give evidence that atmospheric pressure chemical vapor deposition, which relies on gas switching sequences of the reactive gases in a hydrogen ambience, is able to produce interface abruptness comparable if not better than reported by any other technique. 22 refs., 7 figs.

  12. Conversion of carbon dioxide to value-added chemicals in atmospheric pressure dielectric barrier discharges

    NASA Astrophysics Data System (ADS)

    Paulussen, Sabine; Verheyde, Bert; Tu, Xin; De Bie, Christophe; Martens, Tom; Petrovic, Dragana; Bogaerts, Annemie; Sels, Bert

    2010-06-01

    The aim of this work consists of the evaluation of atmospheric pressure dielectric barrier discharges for the conversion of greenhouse gases into useful compounds. Therefore, pure CO2 feed flows are administered to the discharge zone at varying discharge frequency, power input, gas temperature and feed flow rates, aiming at the formation of CO and O2. The discharge obtained in CO2 is characterized as a filamentary mode with a microdischarge zone in each half cycle of the applied voltage. It is shown that the most important parameter affecting the CO2-conversion levels is the gas flow rate. At low flow rates, both the conversion and the CO-yield are significantly higher. In addition, also an increase in the gas temperature and the power input give rise to higher conversion levels, although the effect on the CO-yield is limited. The optimum discharge frequency depends on the power input level and it cannot be unambiguously stated that higher frequencies give rise to increased conversion levels. A maximum CO2 conversion of 30% is achieved at a flow rate of 0.05 L min-1, a power density of 14.75 W cm-3 and a frequency of 60 kHz. The most energy efficient conversions are achieved at a flow rate of 0.2 L min-1, a power density of 11 W cm-3 and a discharge frequency of 30 kHz.

  13. Microstructure characteristics of ZrO2 coating produced by atmospheric pressure chemical vapor deposition.

    PubMed

    Sun, Wei; Xiong, Xiang; Li, Xiaobin

    2011-09-01

    To settle the problem of low growth rate when prepare ZrO2 thermal barrier coating by Metalorganic CVD (MOCVD), a simple method was employed-atmospheric pressure CVD (APCVD). The paper firstly thermodynamic calculated the effect of O/Zr ratio and temperature on phase formation at various H/C ratios for ZrCl4-CO2-H2-Ar system. With temperature increment, the solid phase changes from C+ monoclinic ZrO2 to Monoclinic ZrO2 then to tetragonal ZrO2. With the increase of H/C ratio, the phase zone of C+ monoclinic ZrO2 expands. XRD and Raman spectrum were employed to measure phase structure of ZrO2 coating at different temperature. At 1300 degrees C, the coating contains a small amount tetragonal ZrO2 phase besides monoclinic phase; at 1100 degrees C, the coating is composed of monoclinic ZrO2 phase and a little C. The surface SEM images show the small grains evolve to polycrystals which have clear crystal form when raising temperature. The cross-section images show that dense ZrO2 column crystals arrange normal to the substrate. PMID:22097578

  14. Chemically reactive species in liquids generated by atmospheric-pressure plasmas and their roles in plasma medicine

    SciTech Connect

    Hamaguchi, Satoshi

    2013-07-11

    Plasmas whose gas temperatures are close to room temperature may be generated in ambient air or a gas at atmospheric pressure with the use of low-frequency high voltage or low-power radio-frequency (RF) or microwave power applied to electrodes. Such plasmas can serve as a powerful source of free radicals and/or chemically reactive species that arise from atoms and molecules of the ambient gas. Recently use of such plasmas for medical purposes has attracted much attention as they can be implemented in possible medical devices that can cause blood coagulation, heal wounds, facilitate angiogenesis, sterilize surgical devices as well as living tissues without harming healthy cells, and selectively inactivate cancer cells. Especially of interest among reactive species generated by atmospheric-pressure plasmas (APP) are reactive oxygen species (ROS) and reactive nitrogen species (RNS) that are generated in liquid phase. Since most living tissues and cells are immersed in liquids (such as blood or culture media), reactive species generated by APPs in the gas phase are transported to the liquid phase and possibly converted to different types of reactive species therein before causing some influence on the tissues or cells. In this study, the rate equations are solved to evaluate concentrations of various reactive species in pure water that are originated by plasma reactions in atmosphere and possible effects of such species (including ROS/RNS) on living tissues and cells are discussed.

  15. Chemically reactive species in liquids generated by atmospheric-pressure plasmas and their roles in plasma medicine

    NASA Astrophysics Data System (ADS)

    Hamaguchi, Satoshi

    2013-07-01

    Plasmas whose gas temperatures are close to room temperature may be generated in ambient air or a gas at atmospheric pressure with the use of low-frequency high voltage or low-power radio-frequency (RF) or microwave power applied to electrodes. Such plasmas can serve as a powerful source of free radicals and/or chemically reactive species that arise from atoms and molecules of the ambient gas. Recently use of such plasmas for medical purposes has attracted much attention as they can be implemented in possible medical devices that can cause blood coagulation, heal wounds, facilitate angiogenesis, sterilize surgical devices as well as living tissues without harming healthy cells, and selectively inactivate cancer cells. Especially of interest among reactive species generated by atmospheric-pressure plasmas (APP) are reactive oxygen species (ROS) and reactive nitrogen species (RNS) that are generated in liquid phase. Since most living tissues and cells are immersed in liquids (such as blood or culture media), reactive species generated by APPs in the gas phase are transported to the liquid phase and possibly converted to different types of reactive species therein before causing some influence on the tissues or cells. In this study, the rate equations are solved to evaluate concentrations of various reactive species in pure water that are originated by plasma reactions in atmosphere and possible effects of such species (including ROS/RNS) on living tissues and cells are discussed.

  16. Electrosonic spray ionization. A gentle technique for generating folded proteins and protein complexes in the gas phase and for studying ion-molecule reactions at atmospheric pressure.

    PubMed

    Takáts, Zoltán; Wiseman, Justin M; Gologan, Bogdan; Cooks, R Graham

    2004-07-15

    Electrosonic spray ionization (ESSI), a variant on electrospray ionization (ESI), employs a traditional micro ESI source with supersonic nebulizing gas. The high linear velocity of the nebulizing gas provides efficient pneumatic spraying of the charged liquid sample. The variable electrostatic potential can be tuned to allow efficient and gentle ionization. This ionization method is successfully applied to aqueous solutions of various proteins at neutral pH, and its performance is compared to that of the nanospray and micro ESI techniques. Evidence for efficient desolvation during ESSI is provided by the fact that the peak widths for various multiply charged protein ions are an order of magnitude narrower than those for nanospray. Narrow charge-state distributions compared to other ESI techniques are observed also; for most of the proteins studied, more than 90% of the protein ions can be accumulated in one charge state using ESSI when optimizing conditions. The fact that the abundant charge state is normally as low or lower than that recorded by ESI or nanospray indicates that folded protein ions are generated. The sensitivity of the ionization technique to high salt concentrations is comparable to that of nanospray, but ESSI is considerably less sensitive to high concentrations of organic additives such as glycerol or 2-amino-2-(hydroxymethyl)-1,3-propanediol (Tris base). Noncovalent complexes are observed in the case of myoglobin, protein kinase A/ATP complex, and other proteins. The extent of dissociation of protein ions in ESSI is comparable to or even smaller than that in the case of nanospray, emphasizing the gentle nature of the method. The unique features of ESSI are ascribed to very efficient spraying and the low internal energy supplied to the ions. Evidence is provided that the method is capable of generating fully desolvated protein ions at atmospheric pressure. This allows the technique to be used for the study of ion-molecule reactions at atmospheric

  17. Direct atmospheric pressure chemical ionisation ion trap mass spectrometry for aroma analysis: Speed, sensitivity and resolution of isobaric compounds

    NASA Astrophysics Data System (ADS)

    Jublot, Lionel; Linforth, Robert S. T.; Taylor, Andrew J.

    2005-06-01

    Atmospheric pressure chemical ionisation (APCI) sources were developed for real time analysis of volatile release from foods using an ion trap (IT) mass spectrometer (MS). Key objectives were spectral simplicity (minimal fragmentation), response time and signal to noise ratio. The benefits of APCI-IT-MS were assessed by comparing the performance for in vivo and headspace analyses with that obtained using APCI coupled to a quadrupole mass analyser. Using MS-MS, direct APCI-IT-MS was able to differentiate mixtures of some C6 and terpene isobaric aroma compounds. Resolution could be achieved for some compounds by monitoring specific secondary ions. Direct resolution was also achieved with two of the three isobaric compounds released from chocolate with time as the sample was eaten.

  18. A high temperature and atmospheric pressure experimental and detailed chemical kinetic modelling study of 2-methyl furan oxidation

    PubMed Central

    Somers, Kieran P.; Simmie, John M.; Gillespie, Fiona; Burke, Ultan; Connolly, Jessica; Metcalfe, Wayne K.; Battin-Leclerc, Frédérique; Dirrenberger, Patricia; Herbinet, Olivier; Glaude, Pierre-Alexandre; Curran, Henry J.

    2013-01-01

    An experimental ignition delay time study for the promising biofuel 2-methyl furan (2MF) was performed at equivalence ratios of 0.5, 1.0 and 2.0 for mixtures of 1% fuel in argon in the temperature range 1200–1800 K at atmospheric pressure. Laminar burning velocities were determined using the heat-flux method for mixtures of 2MF in air at equivalence ratios of 0.55–1.65, initial temperatures of 298–398 K and atmospheric pressure. A detailed chemical kinetic mechanism consisting of 2059 reactions and 391 species has been constructed to describe the oxidation of 2MF and is used to simulate experiment. Accurate reproduction of the experimental data has been obtained over all conditions with the developed mechanism. Rate of production and sensitivity analyses have been carried out to identify important consumption pathways of the fuel and key kinetic parameters under these conditions. The reactions of hydrogen atom with the fuel are highlighted as important under all experimental conditions studied, with abstraction by the hydrogen atom promoting reactivity and hydrogen atom addition to the furan ring inhibiting reactivity. This work, to the authors knowledge, is the first to combine theoretical and experimental work to describe the oxidation of any of the alkylated furans. The mechanism developed herein to describe 2MF combustion should also function as a sub-mechanism to describe the oxidation of 2,5-dimethyl furan whilst also providing key insights into the oxidation of this similar biofuel candidate. PMID:23814505

  19. Halo-shaped flowing atmospheric pressure afterglow: a heavenly design for simplified sample introduction and improved ionization in ambient mass spectrometry.

    PubMed

    Pfeuffer, Kevin P; Schaper, J Niklas; Shelley, Jacob T; Ray, Steven J; Chan, George C-Y; Bings, Nicolas H; Hieftje, Gary M

    2013-08-01

    The flowing atmospheric-pressure afterglow (FAPA) is a promising new source for atmospheric-pressure, ambient desorption/ionization mass spectrometry. However, problems exist with reproducible sample introduction into the FAPA source. To overcome this limitation, a new FAPA geometry has been developed in which concentric tubular electrodes are utilized to form a halo-shaped discharge; this geometry has been termed the halo-FAPA or h-FAPA. With this new geometry, it is still possible to achieve direct desorption and ionization from a surface; however, sample introduction through the inner capillary is also possible and improves interaction between the sample material (solution, vapor, or aerosol) and the plasma to promote desorption and ionization. The h-FAPA operates with a helium gas flow of 0.60 L/min outer, 0.30 L/min inner, and applied current of 30 mA at 200 V for 6 W of power. In addition, separation of the discharge proper and sample material prevents perturbations to the plasma. Optical-emission characterization and gas rotational temperatures reveal that the temperature of the discharge is not significantly affected (<3% change at 450 K) by water vapor during solution-aerosol sample introduction. The primary mass-spectral background species are protonated water clusters, and the primary analyte ions are protonated molecular ions (M + H(+)). Flexibility of the new ambient sampling source is demonstrated by coupling it with a laser ablation unit, a concentric nebulizer, and a droplet-on-demand system for sample introduction. A novel arrangement is also presented in which the central channel of the h-FAPA is used as the inlet to a mass spectrometer. PMID:23808829

  20. The effect of dielectric tube diameter on the propagation velocity of ionization waves in a He atmospheric-pressure micro-plasma jet

    NASA Astrophysics Data System (ADS)

    Talviste, Rasmus; Jõgi, Indrek; Raud, Jüri; Paris, Peeter

    2016-05-01

    The focus of this study was to investigate the effect of the dielectric tube diameter on the velocity of the ionization wave in an atmospheric pressure plasma jet in He gas flow. Plasma was ignited in quartz tubes with inner diameter in the range of 80–500 μm by 6 kHz sinusoidal voltage applied to a cylindrical electrode surrounding the quartz tube and positioned 10 mm from the tube orifice. A grounded plane was placed 2–3 cm downstream from the powered electrode to measure the plasma current. The spatial development of ionization waves was monitored by registering the optical emission along the axis of the tube. The ionization wave velocity was deduced from the temporal shift of the onset of radiation at different axial positions. The velocity of ionization wave increased by almost an order of magnitude with the tube diameter decreasing from 500 to 80 μm and was for the 80 μm microtube 1.7 · 105 m s‑1 during the positive half-cycle and 1.45 · 105 m s‑1 during the negative half-cycle.

  1. Effect of Hydrogen in Size-Limited Growth of Graphene by Atmospheric Pressure Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Zhang, Haoran; Zhang, Yanhui; Wang, Bin; Chen, Zhiying; Sui, Yanping; Zhang, Yaqian; Tang, Chunmiao; Zhu, Bo; Xie, Xiaoming; Yu, Guanghui; Jin, Zhi; Liu, Xinyu

    2015-01-01

    Analysis of graphene domain synthesis explains the main graphene growth process. Size-limited graphene growth caused by hydrogen is studied to achieve efficient graphene synthesis. Graphene synthesis on Cu foils via the chemical vapor deposition method using methane as carbon source is limited by high hydrogen concentration. Results indicate that hydrogen affects graphene nucleation, the growth rate, and the final domain size. Considering the role of hydrogen as both activator and etching reagent, we build a model to explain the cause of this low graphene growth rate for high hydrogen partial pressure. A two-step method is proposed to control the graphene nucleation and growth rate separately. Half the time is required to obtain similar domain size compared with single-step synthesis, indicating improved graphene synthesis efficiency. The change of the partial pressure and transmission time between the two steps is a factor that cannot be ignored to control the graphene growth.

  2. Simple method for preparing hydrogenated amorphous silicon films by chemical vapor deposition at atmospheric pressure

    SciTech Connect

    Ellis, F.B. Jr.

    1983-01-01

    An inexpensive one-step method is presented for fabricating hydrogenated amorphous silicon (a-Si:H) films with good photovoltaic properties using chemical vapor deposition (CVD) from a mixture of silane, disilane, trisilane, and higher polysilanes in hydrogen at one atmosphere total pressure. The gas mixture is generated by the action of dilute acid on magnesium silicide and used immediately in the CVD process. Thus, elaborate techniques for handling, transporting or storing the pyrophoric polysilanes are avoided. In addition, the method requires no expensive vacuum or electrical equipment. The conditions necessary for high (approx. =10%) hydrogen incorporation and very high deposition rates (50-100 A/sec) are explained. Experimental parameters are explained and properties as a function of these parameters are shown. The measurements include hydrogen content, optical, electrical and photovoltaic properties of the a-Si:H films. A chemical kinetic model is presented for this and other silane and polysilane CVD systems between about 400 and 600/sup 0/C. Both homogeneous and heterogeneous reactions are considered. The model is derived from homogeneous gas-phase silane and polysilane chemistry and predicts, in agreement with our experiments, that the homogeneous gas-phase chemistry determines the a-Si:H film growth rate under a variety of conditions. The model is sufficiently predictive to be useful in determining appropriate experimental conditions. Stable solar cells are proposed for a-Si:H and fluorine doped tin oxide which can be produced by CVD at very high deposition rates. The unstable a-Si:H/tin oxide interface is eliminated by a very thin layer of titanium nitride and oxide between the a-Si:H and tin oxide.

  3. Determination of bitter orange alkaloids in dietary supplement Standard Reference Materials by liquid chromatography with atmospheric-pressure ionization mass spectrometry.

    PubMed

    Putzbach, Karsten; Rimmer, Catherine A; Sharpless, Katherine E; Wise, Stephen A; Sander, Lane C

    2007-09-01

    A liquid chromatographic atmospheric-pressure ionization electrospray mass spectrometry (LC-API-ES-MS) method has been developed for the determination of five bitter orange alkaloids (synephrine, octopamine, n-methyltyramine, tyramine, and hordenine) in bitter orange-containing dietary supplement standard reference materials (SRMs). The materials represent a variety of natural, extracted, and processed sample matrices. Two extraction techniques were evaluated: pressurized-fluid extraction (PFE) and sonication extraction. The influence of different solvents, extraction temperatures, and pH were investigated for a plant material and a processed sample. The LC method uses a new approach for the separation of highly polar alkaloids. A fluorinated, silica-based stationary phase separated the five alkaloids and the internal standard terbutaline in less than 20 min. This method enabled the determination of the dominant alkaloid synephrine and other minor alkaloids in a variety of dietary supplement SRMs. PMID:17579842

  4. IR/THz Double Resonance Spectroscopy Approach for Remote Chemical Detection at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Tanner, Elizabeth A.; Phillips, Dane J.; De Lucia, Frank C.; Everitt, Henry O.

    2013-06-01

    A remote sensing methodology based on infrared/terahertz (IR/THz) double resonance (DR) spectroscopy is shown to overcome limitations traditionally associated with either IR or THz spectroscopic approaches for detecting trace gases in an atmosphere. The applicability of IR/THz DR spectroscopy is explored by estimating the IR and THz power requirements for detecting a 100 part-per-million-meter cloud of methyl fluoride, methyl chloride, or methyl bromide at ranges up to 1km in three atmospheric windows below 0.3 THz. These prototypical molecules are used to ascertain the dependence of the DR signal-to-noise ratio on IR and THz beam power. A line-tunable CO_2 laser with 100 ps pulse duration generates a DR signature in four rotational transitions on a time scale commensurate with collisional relaxations caused by atmospheric N_2 and O_2. A continuous wave THz beam is frequency tuned to probe one of these rotational transitions so that laser-induced absorption variations in the analyte cloud are detected as temporal power fluctuations synchronized with the laser pulses. A combination of molecule-specific physics and scenario-dependent atmospheric conditions are used to predict the signal-to-noise ratio (SNR) for detecting an analyte as a function of cloud column density. A methodology is presented by which the optimal IR/THz pump/probe frequencies are identified. These estimates show the potential for low concentration chemical detection in a challenging atmospheric scenario with currently available or near term hardware components.

  5. Atmospheric pressure plasma-initiated chemical vapor deposition (AP-PiCVD) of poly(diethylallylphosphate) coating: a char-forming protective coating for cellulosic textile.

    PubMed

    Hilt, Florian; Boscher, Nicolas D; Duday, David; Desbenoit, Nicolas; Levalois-Grützmacher, Joëlle; Choquet, Patrick

    2014-01-01

    An innovative atmospheric pressure chemical vapor deposition method toward the deposition of polymeric layers has been developed. This latter involves the use of a nanopulsed plasma discharge to initiate the free-radical polymerization of an allyl monomer containing phosphorus (diethylallylphosphate, DEAP) at atmospheric pressure. The polymeric structure of the film is evidence by mass spectrometry. The method, highly suitable for the treatment of natural biopolymer substrate, has been carried out on cotton textile to perform the deposition of an efficient and conformal protective coating. PMID:25362895

  6. Continuous Flow Atmospheric Pressure Laser Desorption/Ionization Using a 6–7-µm-Band Mid-Infrared Tunable Laser for Biomolecular Mass Spectrometry

    PubMed Central

    Hiraguchi, Ryuji; Hazama, Hisanao; Senoo, Kenichirou; Yahata, Yukinori; Masuda, Katsuyoshi; Awazu, Kunio

    2014-01-01

    A continuous flow atmospheric pressure laser desorption/ionization technique using a porous stainless steel probe and a 6–7-µm-band mid-infrared tunable laser was developed. This ion source is capable of direct ionization from a continuous flow with a high temporal stability. The 6–7-µm wavelength region corresponds to the characteristic absorption bands of various molecular vibration modes, including O–H, C=O, CH3 and C–N bonds. Consequently, many organic compounds and solvents, including water, have characteristic absorption peaks in this region. This ion source requires no additional matrix, and utilizes water or acetonitrile as the solvent matrix at several absorption peak wavelengths (6.05 and 7.27 µm, respectively). The distribution of multiply-charged peptide ions is extremely sensitive to the temperature of the heated capillary, which is the inlet of the mass spectrometer. This ionization technique has potential for the interface of liquid chromatography/mass spectrometry (LC/MS). PMID:24937686

  7. Atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry of friction modifier additives analyzed directly from base oil solutions.

    PubMed

    Widder, Lukas; Brennerb, Josef; Huttera, Herbert

    2014-01-01

    To develop new products and to apply measures of quality control quick and simple accessibility of additive composition in automo- tive lubrication is important. The aim of this study was to investigate the possibility of analyzing organic friction modifier additives by means of atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry [AP-MALDI-MS] from lubricant solu- tions without the use of additional separation techniques. Analyses of selected friction modifier ethoxylated tallow amines and oleic acid amide were compared using two ionization methods, positive-ion electrospray ionization (ESI) and AP-MALDI, using a LTQ Orbitrap mass spectrometer. Pure additives were characterized from solvent solutions, as well as from synthetic and mineral base oil mixtures. Detected ions of pure additive samples consisted mainly of [M + H]+, but also alkaLi metal adducts [M + Na]+ and [M + K]+ could be seen. Characterizations of blends of both friction modifiers from the base oil mixtures were carried out as well and showed significant inten- sities for several additive peaks. Thus, this work shows a method to directly analyze friction modifier additives used in the automotive industry from an oil blend via the use of AP-MALDI without any further separation steps. The method presented will further simplify the acquisition of data on lubricant composition and additives. Furthermore, it allows the perspective of analyzing additive reaction products directly from formulated oil blends. PMID:25507326

  8. Atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry of friction modifier additives analyzed directly from base oil solutions.

    PubMed

    Widder, Lukas; Brennerb, Josef; Huttera, Herbert

    2014-01-01

    To develop new products and to apply measures of quality control quick and simple accessibility of additive composition in automo- tive lubrication is important. The aim of this study was to investigate the possibility of analyzing organic friction modifier additives by means of atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry [AP-MALDI-MS] from lubricant solu- tions without the use of additional separation techniques. Analyses of selected friction modifier ethoxylated tallow amines and oleic acid amide were compared using two ionization methods, positive-ion electrospray ionization (ESI) and AP-MALDI, using a LTQ Orbitrap mass spectrometer. Pure additives were characterized from solvent solutions, as well as from synthetic and mineral base oil mixtures. Detected ions of pure additive samples consisted mainly of [M + H]+, but also alkaLi metal adducts [M + Na]+ and [M + K]+ could be seen. Characterizations of blends of both friction modifiers from the base oil mixtures were carried out as well and showed significant inten- sities for several additive peaks. Thus, this work shows a method to directly analyze friction modifier additives used in the automotive industry from an oil blend via the use of AP-MALDI without any further separation steps. The method presented will further simplify the acquisition of data on lubricant composition and additives. Furthermore, it allows the perspective of analyzing additive reaction products directly from formulated oil blends. PMID:25420342

  9. Continuous flow atmospheric pressure laser desorption/ionization using a 6-7-µm-band mid-infrared tunable laser for biomolecular mass spectrometry.

    PubMed

    Hiraguchi, Ryuji; Hazama, Hisanao; Senoo, Kenichirou; Yahata, Yukinori; Masuda, Katsuyoshi; Awazu, Kunio

    2014-01-01

    A continuous flow atmospheric pressure laser desorption/ionization technique using a porous stainless steel probe and a 6-7-µm-band mid-infrared tunable laser was developed. This ion source is capable of direct ionization from a continuous flow with a high temporal stability. The 6-7-µm wavelength region corresponds to the characteristic absorption bands of various molecular vibration modes, including O-H, C=O, CH3 and C-N bonds. Consequently, many organic compounds and solvents, including water, have characteristic absorption peaks in this region. This ion source requires no additional matrix, and utilizes water or acetonitrile as the solvent matrix at several absorption peak wavelengths (6.05 and 7.27 µm, respectively). The distribution of multiply-charged peptide ions is extremely sensitive to the temperature of the heated capillary, which is the inlet of the mass spectrometer. This ionization technique has potential for the interface of liquid chromatography/mass spectrometry (LC/MS). PMID:24937686

  10. A comparative study of APLI and APCI in IMS at atmospheric pressure to reveal and explain peak broadening effects by the use of APLI.

    PubMed

    Ihlenborg, Marvin; Raupers, Björn; Gunzer, Frank; Grotemeyer, Jürgen

    2015-11-21

    The details of the ionization mechanism in atmospheric pressure are still not completely known. In order to obtain further insight into the occurring processes in atmospheric pressure laser ionization (APLI) a comparative study of atmospheric pressure chemical ionization (APCI) and APLI is presented in this paper. This study is carried out using similar experimental condition at atmospheric pressure employing a commercial ion mobility spectrometer (IMS). Two different peak broadening mechanisms can then be assigned, one related to a range of different species generated and detected, and furthermore for the first time a power broadening effect on the signals can be identified. PMID:26421367

  11. Determination of sulfonamides by packed column supercritical fluid chromatography with atmospheric pressure chemical ionisation mass spectrometric detection.

    PubMed

    Dost, K; Jones, D C; Davidson, G

    2000-07-01

    Sulfonamide antibiotics are widely used to prevent bacterial infections in livestock, and residues are commonly found in milk and meat. Packed column supercritical fluid chromatography (pSFC) with detection using ultra violet (UV) and atmospheric pressure chemical ionisation (APCI) mass spectrometry (MS) provides a versatile method for the detection and quantification of six major sulfonamides. The APCI mass spectra for all the sulfonamides consisted of protonated molecules at low cone voltages. Increasing the cone voltage led to informative fragmentation patterns, which provided structural information for identification purposes. The pSFC-APCI-MS technique was shown to be linear (r2 > or = 0.999) over the concentration range 0.1-50 micrograms ml-1 using total ion current. The precision and the accuracy of the system and validation of sample preparation are acceptable, with RSD < 2% and relative error 8%. Selected ion monitoring gave detection limits as follows: sulfadiazine 41, sulfamethoxazole 45, sulfamerazine 47, sulfamethizole 59, sulfamethazine 181 and sulfadimethoxine 96 micrograms l-1, which are lower than the amounts permitted in milk products. The APCI pSFC-MS system was shown to have a high degree of reproducibility. The technique was then applied to determine the above sulfonamides in milk. The results obtained show that there are no matrix effects from the milk and that the detection limits remained as stated for the standard solutions. PMID:10984919

  12. Photocatalytic Functional Coating of TiO2 Thin Film Deposited by Cyclic Plasma Chemical Vapor Deposition at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Kwon, Jung-Dae; Rha, Jong-Joo; Nam, Kee-Seok; Park, Jin-Seong

    2011-08-01

    Photocatalytic TiO2 thin films were prepared with titanium tetraisopropoxide (TTIP) using cyclic plasma chemical vapor deposition (CPCVD) at atmospheric pressure. The CPCVD TiO2 films contain carbon-free impurities up to 100 °C and polycrystalline anatase phases up to 200 °C, due to the radicals and ion-bombardments. The CPCVD TiO2 films have high transparency in the visible wavelength region and absorb wavelengths below 400 nm (>3.2 eV). The photocatalytic effects of the CPCVD TiO2 and commercial sprayed TiO2 films were measured by decomposing methylene blue (MB) solution under UV irradiation. The smooth CPCVD TiO2 films showed a relatively lower photocatalytic efficiency, but superior catalyst-recycling efficiency, due to their high adhesion strength on the substrates. This CPCVD technique may provide the means to produce photocatalytic thin films with low cost and high efficiency, which would be a reasonable candidate for practical photocatalytic applications, because of the reliability and stability of their photocatalytic efficiency in a practical environment.

  13. Investigation on growth behavior of CNTs synthesized by atmospheric pressure plasma enhanced chemical vapor deposition system on Fe catalyzed substrate.

    PubMed

    Choi, Bum Ho; Kim, Won Jae; Kim, Young Baek; Lee, Jong Ho; Park, Jong Woon; Kim, Woo Sam; Shin, Dong Chan

    2008-10-01

    We have studied growth behavior of carbon nanotubes (CNTs) on iron (Fe) catalyzed substrate using newly developed atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) system. To investigate the improved growth performance with simple equipment and process on large scale, a new AP-PECVD system containing different concept on downstream gas was designed and manufactured. As a catalyst, either sputtered or evaporated Fe thin film on SiO2/Si substrate was used and acetylene gas was used as a carbon source. We observed growth behavior of CNTs such as height, rate and density were strongly affected by plasma power. The maximum height of 427 microm and 267 microm was synthesized under RF plasma power of 30 W for 30 min and 40 W for 3 min, respectively. The growth rate dramatically increased to 6.27 times as plasma power increased from 30 to 40 W which opens the possibility the mass production of CNTs. By SEM and TEM observation, it was verified the grown CNTs was consists of mixture of single-wall and multi-wall CNTs. The graphitization ratio was measured to be 0.93, indicating that the graphitized CNTs forest was formed and relatively high purity of CNTs was synthesized, being useful for nano-composite materials to reinforce the strength. From our experiments, we can observe that the height and growth rate of CNTs is strong function of plasma power. PMID:19198378

  14. Various Shapes of ZnO and CdO Nanostructures Grown by Atmospheric-Pressure Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Terasako, Tomoaki; Fujiwara, Tetsuro; Yagi, Masakazu; Shirakata, Sho

    2011-01-01

    Various shapes of ZnO and CdO nanostructures were successfully grown on a- and c-plane sapphire substrates coated with Au nanocolloidal solution by atmospheric-pressure chemical vapor deposition methods under a simultaneous source supply of metal powder (Zn or Cd) and H2O. The ZnO and CdO nanorods (NRs) grown at higher substrate temperatures (TSs) exhibited tapered shapes, resulting from the competition between the axial growth due to the vapor-liquid-solid (VLS) mechanism and the radial growth due to the vapor-solid (VS) mechanism. The alternate source supply of Zn and H2O was found to be effective for suppressing the tapering of ZnO NRs. The appearance of the Y- and T-shaped nanotrees of CdO may be due to the splitting and migration of catalytic particles during the growth process. These results suggest that both the source supply sequence and the substrate temperature are important factors for the shape design of oxide nanostructures.

  15. Fast transient analysis and first-stage collision-induced dissociation with the flowing atmospheric-pressure afterglow ionization source to improve analyte detection and identification.

    PubMed

    Shelley, Jacob T; Hieftje, Gary M

    2010-04-01

    The recent development of ambient desorption/ionization mass spectrometry (ADI-MS) has enabled fast, simple analysis of many different sample types. The ADI-MS sources have numerous advantages, including little or no required sample pre-treatment, simple mass spectra, and direct analysis of solids and liquids. However, problems of competitive ionization and limited fragmentation require sample-constituent separation, high mass accuracy, and/or tandem mass spectrometry (MS/MS) to detect, identify, and quantify unknown analytes. To maintain the inherent high throughput of ADI-MS, it is essential for the ion source/mass analyzer combination to measure fast transient signals and provide structural information. In the current study, the flowing atmospheric-pressure afterglow (FAPA) ionization source is coupled with a time-of-flight mass spectrometer (TOF-MS) to analyze fast transient signals (<500 ms FWHM). It was found that gas chromatography (GC) coupled with the FAPA source resulted in a reproducible (<5% RSD) and sensitive (detection limits of <6 fmol for a mixture of herbicides) system with analysis times of ca. 5 min. Introducing analytes to the FAPA in a transient was also shown to significantly reduce matrix effects caused by competitive ionization by minimizing the number and amount of constituents introduced into the ionization source. Additionally, MS/MS with FAPA-TOF-MS, enabling analyte identification, was performed via first-stage collision-induced dissociation (CID). Lastly, molecular and structural information was obtained across a fast transient peak by modulating the conditions that caused the first-stage CID. PMID:20349535

  16. Comparison of electrospray ionization and atmospheric pressure photoionization liquid chromatography mass spectrometry methods for analysis of ergot alkaloids from endophyte-infected sleepygrass (Achnatherum robustum).

    PubMed

    Jarmusch, Alan K; Musso, Ashleigh M; Shymanovich, Tatsiana; Jarmusch, Scott A; Weavil, Miranda J; Lovin, Mary E; Ehrmann, Brandie M; Saari, Susanna; Nichols, David E; Faeth, Stanley H; Cech, Nadja B

    2016-01-01

    Ergot alkaloids are mycotoxins with an array of biological effects. With this study, we investigated for the first time the application of atmospheric pressure photoionization (APPI) as an ionization method for LC-MS analysis of ergot alkaloids, and compared its performance to that of the more established technique of electrospray ionization (ESI). Samples of the grass Achnatherum robustum infected with the ergot producing Epichloë fungus were extracted using cold methanol and subjected to reserved-phase HPLC-ESI-MS and HPLC-APPI-MS analysis. The ergot alkaloids ergonovine and lysergic acid amide were detected in these samples, and quantified via external calibration. Validation parameters were recorded in accordance with ICH guidelines. A triple quadrupole MS operated in multiple reaction monitoring yielded the lowest detection limits. The performance of APPI and ESI methods was comparable. Both methods were subject to very little matrix interference, with percent recoveries ranging from 82% to 100%. As determined with HPLC-APPI-MS quantification, lysergic acid amide and ergonovine were extracted from an A. robustum sample infected with the Epichloë fungus at concentrations of 1.143±0.051 ppm and 0.2822±0.0071 ppm, respectively. There was no statistically significant difference between these concentrations and those determined using ESI for the same samples. PMID:26340558

  17. Synthesis and modeling of uniform complex metal oxides by close-proximity atmospheric pressure chemical vapor deposition.

    PubMed

    Hoye, Robert L Z; Muñoz-Rojas, David; Musselman, Kevin P; Vaynzof, Yana; MacManus-Driscoll, Judith L

    2015-05-27

    A close-proximity atmospheric pressure chemical vapor deposition (AP-CVD) reactor is developed for synthesizing high quality multicomponent metal oxides for electronics. This combines the advantages of a mechanically controllable substrate-manifold spacing and vertical gas flows. As a result, our AP-CVD reactor can rapidly grow uniform crystalline films on a variety of substrate types at low temperatures without requiring plasma enhancements or low pressures. To demonstrate this, we take the zinc magnesium oxide (Zn(1-x)Mg(x)O) system as an example. By introducing the precursor gases vertically and uniformly to the substrate across the gas manifold, we show that films can be produced with only 3% variation in thickness over a 375 mm(2) deposition area. These thicknesses are significantly more uniform than for films from previous AP-CVD reactors. Our films are also compact, pinhole-free, and have a thickness that is linearly controllable by the number of oscillations of the substrate beneath the gas manifold. Using photoluminescence and X-ray diffraction measurements, we show that for Mg contents below 46 at. %, single phase Zn(1-x)Mg(x)O was produced. To further optimize the growth conditions, we developed a model relating the composition of a ternary oxide with the bubbling rates through the metal precursors. We fitted this model to the X-ray photoelectron spectroscopy measured compositions with an error of Δx = 0.0005. This model showed that the incorporation of Mg into ZnO can be maximized by using the maximum bubbling rate through the Mg precursor for each bubbling rate ratio. When applied to poly(3-hexylthiophene-2,5-diyl) hybrid solar cells, our films yielded an open-circuit voltage increase of over 100% by controlling the Mg content. Such films were deposited in short times (under 2 min over 4 cm(2)). PMID:25939729

  18. Synthesis of Diamond-Like Carbon Films on Planar and Non-Planar Geometries by the Atmospheric Pressure Plasma Chemical Vapor Deposition Method

    NASA Astrophysics Data System (ADS)

    Noborisaka, Mayui; Hirako, Tomoaki; Shirakura, Akira; Watanabe, Toshiyuki; Morikawa, Masashi; Seki, Masaki; Suzuki, Tetsuya

    2012-09-01

    Diamond-like carbon (DLC) films were synthesized by the dielectric barrier discharge-based plasma deposition at atmospheric pressure and their hardness and gas barrier properties were measured. A decrease in size of grains and heating substrate temperature improved nano-hardness up to 3.3 GPa. The gas barrier properties of DLC-coated poly(ethylene terephthalate) (PET) sheets were obtained by 3-5 times of non-coated PET with approximately 0.5 µm in film thickness. The high-gas-barrier DLC films deposited on PET sheets are expected to wrap elevated bridge of the super express and prevent them from neutralization of concrete. We also deposited DLC films inside PET bottles by the microwave surface-wave plasma chemical vapor deposition (CVD) method at near-atmospheric pressure. Under atmospheric pressure, the films were coated uniformly inside the PET bottles, but did not show high gas barrier properties. In this paper, we summarize recent progress of DLC films synthesized at atmospheric pressure with the aimed of food packaging and concrete pillar.

  19. Determination of the dopamine D2 agonist N-0923 and its major metabolites in perfused rat livers by HPLC-UV-atmospheric pressure ionization mass spectrometry.

    PubMed

    Swart, P J; Oelen, W E; Bruins, A P; Tepper, P G; de Zeeuw, R A

    1994-01-01

    The metabolism of the dopamine D2 agonist N-0923 was investigated by an in vitro isolated liver perfusion. Determining the metabolic profile and identity of the different metabolites was achieved by using high-performance liquid chromatography with UV detection, combined with atmospheric pressure ionization mass spectrometry. Using this technique, no extensive sample cleanup is required, and the studies can be performed without radioactivity. In addition to previously observed metabolites, nine new metabolic products were identified. All metabolites were exclusively excreted into the bile, except for the despropyl metabolite, which was also detectable in the perfusate. 5-O-Glucuronidation and N-depropylation followed by 5-O-glucuronidation are the most important metabolic routes. N-dealkylation of the thienylethyl group followed by 5-O-glucuronidation and sulfation is a second major metabolic pathway. Catechol formation of the despropyl metabolite with or without subsequent conjugation was not found. Catechol formation of the desthienylethyl metabolite occurred, but only its glucuronide conjugates were found. This study complements previous results of in vivo metabolic studies using the radiolabeled racemate N-0437, and it explains differences in bile excretion during isolated liver perfusions using N-0923 and radiolabeled N-0923. PMID:7911536

  20. Liquid Sampling-Atmospheric Pressure Glow Discharge (LS-APGD) Ionization Source for Elemental Mass Spectrometry: Preliminary Parametric Evaluation and Figures of Merit

    SciTech Connect

    Quarles, C. Derrick; Carado, Anthony J.; Barinaga, Charles J.; Koppenaal, David W.; Marcus, R. Kenneth

    2012-01-01

    A new, low power ionization source for the elemental analysis of aqueous solutions has recently been described. The liquid sampling-atmospheric pressure glow discharge (LS-APGD) source operates at relatively low currents (<20 mA) and solution flow rates (<50 μL min-1), yielding a relatively simple alternative for atomic mass spectrometry applications. The LS-APGD has been interfaced to what is otherwise an organic, LC-MS mass analyzer, the Thermo Scientific Exactive Orbitrap without any modifications; other than removing the electrospray ionization (ESI) source supplied with that instrument. A glow discharge is initiated between the surface of the test solution exiting a glass capillary and a metallic counter electrode mounted at a 90° angle and separated by a distance of ~5 mm. As with any plasma-based ionization source, there are key discharge operation and ion sampling parameters that affect the intensity and composition of the derived mass spectra; including signal-to-background ratios. We describe here a preliminary parametric evaluation of the roles of discharge current, solution flow rate, argon sheath gas flow rate, and ion sampling distance as they apply on this mass analyzer system. A cursive evaluation of potential matrix effects due to the presence of easily ionized elements (EIEs) indicate that sodium concentrations of up to 500 μg mL-1 generally cause suppressions of less than 50%, dependant upon the analyte species. Based on the results of this series of studies, preliminary limits of detection (LOD) have been established through the generation of calibration functions. Whilst solution-based concentrations LOD levels of 0.02 – 2 μg mL-1 3 are not impressive on the surface, the fact that they are determined via discrete 5 μL injections leads to mass-based detection limits at picogram to singlenanogram levels. The overhead costs associated with source operation (10 W d.c. power, solution flow rates of <50 μL min-1, and gas flow rates <10 mL min

  1. Liquid sampling-atmospheric pressure glow discharge (LS-APGD) ionization source for elemental mass spectrometry: preliminary parametric evaluation and figures of merit.

    PubMed

    Quarles, C Derrick; Carado, Anthony J; Barinaga, Charles J; Koppenaal, David W; Marcus, R Kenneth

    2012-01-01

    A new, low-power ionization source for the elemental analysis of aqueous solutions has recently been described. The liquid sampling-atmospheric pressure glow discharge (LS-APGD) source operates at relatively low currents (<20 mA) and solution flow rates (<50 μL min(-1)), yielding a relatively simple alternative for atomic mass spectrometry applications. The LS-APGD has been interfaced to what is otherwise an organic, LC-MS mass analyzer, the Thermo Scientific Exactive Orbitrap without any modifications, other than removing the electrospray ionization source supplied with that instrument. A glow discharge is initiated between the surface of the test solution exiting a glass capillary and a metallic counter electrode mounted at a 90° angle and separated by a distance of ~5 mm. As with any plasma-based ionization source, there are key discharge operation and ion sampling parameters that affect the intensity and composition of the derived mass spectra, including signal-to-background ratios. We describe here a preliminary parametric evaluation of the roles of discharge current, solution flow rate, argon sheath gas flow rate, and ion sampling distance as they apply on this mass analyzer system. A cursive evaluation of potential matrix effects due to the presence of easily ionized elements indicate that sodium concentrations of up to 50 μg mL(-1) generally cause suppressions of less than 50%, dependant upon the analyte species. Based on the results of this series of studies, preliminary limits of detection (LOD) have been established through the generation of calibration functions. While solution-based concentration LOD levels of 0.02-2 μg mL(-1) are not impressive on the surface, the fact that they are determined via discrete 5 μL injections leads to mass-based detection limits at picogram to single-nanogram levels. The overhead costs associated with source operation (10 W d.c. power, solution flow rates of <50 μL min(-1), and gas flow rates <10 mL min(-1)) are

  2. Breaking the pumping speed barrier in mass spectrometry: discontinuous atmospheric pressure interface.

    PubMed

    Gao, Liang; Cooks, R Graham; Ouyang, Zheng

    2008-06-01

    The performance of mass spectrometers with limited pumping capacity is shown to be improved through use of a discontinuous atmospheric pressure interface (DAPI). A proof-of-concept DAPI interface was designed and characterized using a miniature rectilinear ion trap mass spectrometer. The interface consists of a simple capillary directly connecting the atmospheric pressure ion source to the vacuum mass analyzer region; it has no ion optical elements and no differential pumping stages. Gases carrying ionized analytes were pulsed into the mass analyzer for short periods at high flow rates rather than being continuously introduced at lower flow rates; this procedure maximized ion transfer. The use of DAPI provides a simple solution to the problem of coupling an atmospheric pressure ionization source to a miniature instrument with limited pumping capacity. Data were recorded using various atmospheric pressure ionization sources, including electrospray ionization (ESI), nano-ESI, atmospheric pressure chemical ionization (APCI), and desorption electrospray ionization (DESI) sources. The interface was opened briefly for ion introduction during each scan. With the use of the 18 W pumping system of the Mini 10, limits of detection in the low part-per-billion levels were achieved and unit resolution mass spectra were recorded. PMID:18461971

  3. Quantitative Analysis of Mixed Halogen Dioxins and Furans in Fire Debris Utilizing Atmospheric Pressure Ionization Gas Chromatography-Triple Quadrupole Mass Spectrometry.

    PubMed

    Organtini, Kari L; Myers, Anne L; Jobst, Karl J; Reiner, Eric J; Ross, Brian; Ladak, Adam; Mullin, Lauren; Stevens, Douglas; Dorman, Frank L

    2015-10-20

    Residential and commercial fires generate a complex mixture of volatile, semivolatile, and nonvolatile compounds. This study focused on the semi/nonvolatile components of fire debris to better understand firefighter exposure risks. Using the enhanced sensitivity of gas chromatography coupled to atmospheric pressure ionization-tandem mass spectrometry (APGC-MS/MS), complex fire debris samples collected from simulation fires were analyzed for the presence of potentially toxic polyhalogenated dibenzo-p-dioxins and dibenzofurans (PXDD/Fs and PBDD/Fs). Extensive method development was performed to create multiple reaction monitoring (MRM) methods for a wide range of PXDD/Fs from dihalogenated through hexa-halogenated homologue groups. Higher halogenated compounds were not observed due to difficulty eluting them off the long column used for analysis. This methodology was able to identify both polyhalogenated (mixed bromo-/chloro- and polybromo-) dibenzo-p-dioxins and dibenzofurans in the simulated burn study samples collected, with the dibenzofuran species being the dominant compounds in the samples. Levels of these compounds were quantified as total homologue groups due to the limitations of commercial congener availability. Concentration ranges in household simulation debris were observed at 0.01-5.32 ppb (PXDFs) and 0.18-82.11 ppb (PBDFs). Concentration ranges in electronics simulation debris were observed at 0.10-175.26 ppb (PXDFs) and 0.33-9254.41 ppb (PBDFs). Samples taken from the particulate matter coating the firefighters' helmets contained some of the highest levels of dibenzofurans, ranging from 4.10 ppb to 2.35 ppm. The data suggest that firefighters and first responders at fire scenes are exposed to a complex mixture of potentially hundreds to thousands of different polyhalogenated dibenzo-p-dioxins and dibenzofurans that could negatively impact their health. PMID:26412694

  4. Quantification and remote detection of nitro explosives by helium plasma ionization mass spectrometry (HePI-MS) on a modified atmospheric pressure source designed for electrospray ionization.

    PubMed

    Yang, Zhihua; Pavlov, Julius; Attygalle, Athula B

    2012-07-01

    Helium Plasma Ionization (HePI) generates gaseous negative ions upon exposure of vapors emanating from organic nitro compounds. A simple adaptation converts any electrospray ionization source to a HePI source by passing helium through the sample delivery metal capillary held at a negative potential. Compared with the demands of other He-requiring ambient pressure ionization sources, the consumption of helium by the HePI source is minimal (20-30 ml/min). Quantification experiments conducted by exposing solid deposits to a HePI source revealed that 1 ng of 2,4,6-trinitrotoluene (TNT) on a filter paper (about 0.01 ng/mm(2)) could be detected by this method. When vapor emanating from a 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) sample was subjected to helium plasma ionization mass spectrometry (HePI-MS), a peak was observed at m/z 268 for (RDX●NO(2))(-). This facile formation of NO(2)(-) adducts was noted without the need of any extra additives as dopants. Quantitative evaluations showed RDX detection by HePI-MS to be linear over at least three orders of magnitude. TNT samples placed even 5 m away from the source were detected when the sample headspace vapor was swept by a stream of argon or nitrogen and delivered to the helium plasma ion source via a metal tube. Among the tubing materials investigated, stainless steel showed the best performance for sample delivery. A system with a copper tube, and air as the carrier gas, for example, failed to deliver any detectable amount of TNT to the source. In fact, passing over hot copper appears to be a practical way of removing TNT or other nitroaromatics from ambient air. PMID:22791251

  5. Atmospheric-pressure plasma jet

    DOEpatents

    Selwyn, Gary S.

    1999-01-01

    Atmospheric-pressure plasma jet. A .gamma.-mode, resonant-cavity plasma discharge that can be operated at atmospheric pressure and near room temperature using 13.56 MHz rf power is described. Unlike plasma torches, the discharge produces a gas-phase effluent no hotter than 250.degree. C. at an applied power of about 300 W, and shows distinct non-thermal characteristics. In the simplest design, two concentric cylindrical electrodes are employed to generate a plasma in the annular region therebetween. A "jet" of long-lived metastable and reactive species that are capable of rapidly cleaning or etching metals and other materials is generated which extends up to 8 in. beyond the open end of the electrodes. Films and coatings may also be removed by these species. Arcing is prevented in the apparatus by using gas mixtures containing He, which limits ionization, by using high flow velocities, and by properly shaping the rf-powered electrode. Because of the atmospheric pressure operation, no ions survive for a sufficiently long distance beyond the active plasma discharge to bombard a workpiece, unlike low-pressure plasma sources and conventional plasma processing methods.

  6. Low temperature carrier transport study of monolayer MoS{sub 2} field effect transistors prepared by chemical vapor deposition under an atmospheric pressure

    SciTech Connect

    Liu, Xinke E-mail: wujing026@gmail.com; He, Jiazhu; Tang, Dan; Lu, Youming; Zhu, Deliang; Liu, Wenjun; Cao, Peijiang; Han, Sun; Liu, Qiang; Wen, Jiao; Yu, Wenjie; Liu, Wenjun; Wu, Jing E-mail: wujing026@gmail.com; He, Zhubing; Ang, Kah-Wee

    2015-09-28

    Large size monolayer Molybdenum disulphide (MoS{sub 2}) was successfully grown by chemical vapor deposition method under an atmospheric pressure. The electrical transport properties of the fabricated back-gate monolayer MoS{sub 2} field effect transistors (FETs) were investigated under low temperatures; a peak field effect mobility of 59 cm{sup 2}V{sup −1}s{sup −1} was achieved. With the assist of Raman measurement under low temperature, this work identified the mobility limiting factor for the monolayer MoS{sub 2} FETs: homopolar phonon scattering under low temperature and electron-polar optical phonon scattering at room temperature.

  7. Development of open air silicon deposition technology by silane-free atmospheric pressure plasma enhanced chemical transport under local ambient gas control

    NASA Astrophysics Data System (ADS)

    Naito, Teruki; Konno, Nobuaki; Yoshida, Yukihisa

    2016-07-01

    Open air silicon deposition was performed by combining silane-free atmospheric pressure plasma-enhanced chemical transport and a newly developed local ambient gas control technology. The effect of air contamination on silicon deposition was investigated using a vacuum chamber, and the allowable air contamination level was confirmed to be 3 ppm. The capability of the local ambient gas control head was investigated numerically and experimentally. A safe and clean process environment with air contamination less than 1 ppm was achieved. Combining these technologies, a microcrystalline silicon film was deposited in open air, the properties of which were comparable to those of silicon films deposited in a vacuum chamber.

  8. Identification of main corticosteroids as illegal feed additives in milk replacers by liquid chromatography-atmospheric pressure chemical ionisation mass spectrometry.

    PubMed

    Fiori, M; Pierdominici, E; Longo, F; Brambilla, G

    1998-05-22

    Corticosteroids were proposed as growth promoting agents to improve commercial quality of meat. We developed a liquid chromatography-atmospheric pressure chemical ionisation mass spectrometry (LC-APCI-MS) method able to identify the presence in milk replacers, when given by mouth, of dexamethasone, betamethasone, flumethasone, triamcinolone, predinisotone, prednisolone, methylprednisolone, fludrocortisone and beclomethasone, at levels in the range of 20-100 ppb. C18 solid-phase extraction, LC-RP C8 column separation, data acquisition (positive ions) in the scan range m/z 200-550 allowed us to differentiate and identify compounds by protonated molecules, their methanolic adducts and fragmentation patterns. PMID:9646497

  9. Chemical protection against ionizing radiation

    NASA Astrophysics Data System (ADS)

    Maisin, J. R.

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

  10. Atmospheric pressure plasma chemical vapor deposition reactor for 100 mm wafers, optimized for minimum contamination at low gas flow rates

    SciTech Connect

    Anand, Venu E-mail: venuanand83@gmail.com; Shivashankar, S. A.; Nair, Aswathi R.; Mohan Rao, G.

    2015-08-31

    Gas discharge plasmas used for thinfilm deposition by plasma-enhanced chemical vapor deposition (PECVD) must be devoid of contaminants, like dust or active species which disturb the intended chemical reaction. In atmospheric pressure plasma systems employing an inert gas, the main source of such contamination is the residual air inside the system. To enable the construction of an atmospheric pressure plasma (APP) system with minimal contamination, we have carried out fluid dynamic simulation of the APP chamber into which an inert gas is injected at different mass flow rates. On the basis of the simulation results, we have designed and built a simple, scaled APP system, which is capable of holding a 100 mm substrate wafer, so that the presence of air (contamination) in the APP chamber is minimized with as low a flow rate of argon as possible. This is examined systematically by examining optical emission from the plasma as a function of inert gas flow rate. It is found that optical emission from the plasma shows the presence of atmospheric air, if the inlet argon flow rate is lowered below 300 sccm. That there is minimal contamination of the APP reactor built here, was verified by conducting an atmospheric pressure PECVD process under acetylene flow, combined with argon flow at 100 sccm and 500 sccm. The deposition of a polymer coating is confirmed by infrared spectroscopy. X-ray photoelectron spectroscopy shows that the polymer coating contains only 5% of oxygen, which is comparable to the oxygen content in polymer deposits obtained in low-pressure PECVD systems.

  11. On-line measurements of α-pinene ozonolysis products using an atmospheric pressure chemical ionisation ion-trap mass spectrometer

    NASA Astrophysics Data System (ADS)

    Warscheid, Bettina; Hoffmann, Thorsten

    An on-line technique to investigate complex organic oxidation reactions in environmental chamber experiments is presented. The method is based on the direct introduction of the chamber air into an atmospheric pressure ion source of a commercial ion-trap mass spectrometer. To demonstrate the analytical potential of the method (atmospheric pressure chemical ionisation/mass spectrometry, APCI/MS), the ozonolysis of α-pinene was investigated in a series of experiments performed in various sized reaction chambers at atmospheric pressure and 296 K in synthetic air. Investigations were focussed on the influence of the water vapour concentration on the formation of the predominant oxidation product, pinonaldehyde, derived from the α-pinene/ozone reaction. Quantification of pinonaldehyde was achieved by conducting a standard addition technique. The molar yield of pinonaldehyde was found to depend strongly on the actual water vapour concentration between <1 and 80% relative humidity. Starting with an average yield of 0.23±0.05 at dry conditions, pinonaldehyde formation was approximately doubled by reaching a yield of 0.53±0.05 at a relative humidity of around 60%. Furthermore, the formation mechanism of pinonaldehyde was investigated in greater detail using isotopically labelled water. Applying on-line APCI/MS, pinonaldehyde formation under incorporation of 18O was observed, strongly supporting the reaction of the stabilised Criegee radical with water in the gas phase as suggested by Alvarado et al. (Journal of Geophysical Research 103 (1998) 25541-25551). Furthermore, the mass spectra recorded on-line were used to perform a semi-quantitative estimation of the decomposition pathway of the primary ozonide, indicating a branching ratio of 0.35/0.65.

  12. Special issue: diagnostics of atmospheric pressure microplasmas

    NASA Astrophysics Data System (ADS)

    Bruggeman, Peter; Czarnetzki, Uwe; Tachibana, Kunihide

    2013-11-01

    In recent decades, a strong revival of non-equilibrium atmospheric pressure plasma studies has developed in the form of microplasmas. Microplasmas have typical scales of 1 mm or less and offer a very exciting research direction in the field of plasma science and technology as the discharge physics can be considerably different due to high collisionality and the importance of plasma-surface interaction. These high-pressure small-scale plasmas have a diverse range of physical and chemical properties. This diversity coincides with various applications including light/UV sources [1], material processing [2], chemical analysis [3], material synthesis [4], electromagnetics [5], combustion [6] and even medicine [7]. At atmospheric pressure, large scale plasmas have the tendency to become unstable due to the high collision rates leading to enhanced heating and ionization compared to their low-pressure counterparts. As low-pressure plasmas typically operate in reactors with sizes of tens of centimetres, scaling up the pressure to atmospheric pressure the size of the plasma reduces to typical sizes below 1 mm. A natural approach of stabilizing atmospheric pressure plasmas is thus the use of microelectrode geometries. Traditionally microplasmas have been produced in confined geometries which allow one to stabilize dc excited discharges. This stabilization is intrinsically connected to the large surface-to-volume ratio which enhances heat transfer and losses of charged and excited species to the walls. Currently challenging boundaries are pushed by producing microcavity geometries with dimensions of the order of 1 µm [8]. The subject of this special issue, diagnostics of microplasmas, is motivated by the many challenges in microplasma diagnostics in view of the complex chemistry and strong spatial (and even temporal) gradients of species densities and plasma properties. Atmospheric pressure plasmas have a very long history dating back more than 100 years, with early work of

  13. Skeletal muscle fiber analysis by atmospheric pressure scanning microprobe matrix-assisted laser desorption/ionization mass spectrometric imaging at high mass and high spatial resolution.

    PubMed

    Tsai, Yu-Hsuan; Bhandari, Dhaka Ram; Garrett, Timothy J; Carter, Christy S; Spengler, Bernhard; Yost, Richard A

    2016-06-01

    Skeletal muscles are composed of heterogeneous muscle fibers with various fiber types. These fibers can be classified into different classes based on their different characteristics. MALDI mass spectrometric imaging (MSI) has been applied to study and visualize different metabolomics profiles of different fiber types. Here, skeletal muscles were analyzed by atmospheric pressure scanning microprobe MALDI-MSI at high spatial and high mass resolution. PMID:27198224

  14. Atmospheric Pressure Chemical Vapor Deposition of High Silica SiO2-TiO2 Antireflective Thin Films for Glass Based Solar Panels

    SciTech Connect

    Klobukowski, Erik R; Tenhaeff, Wyatt E; McCamy, James; Harris, Caroline; Narula, Chaitanya Kumar

    2013-08-30

    The atmospheric pressure chemical vapor deposition (APCVD) of SiO2-TiO2 thin films employing [[(tBuO)3Si]2O-Ti(OiPr)2], which can be prepared from commercially available materials, results in antireflective thin films on float glass under industrially relevant manufacturing conditions. It was found that while the deposition temperature had an effect on the SiO2:TiO2 ratio, the thickness was dependent on the time of deposition. This study shows that it is possible to use APCVD employing a single source precursor containing titanium and silicon to produce thin films on float glass with high SiO2:TiO2 ratios.

  15. Structural elucidation of monoterpene oxidation products by ion trap fragmentation using on-line atmospheric pressure chemical ionisation mass spectrometry in the negative ion mode.

    PubMed

    Warscheid, B; Hoffmann, T

    2001-01-01

    Based on ion trap mass spectrometry, an on-line method is described which provides valuable information on the molecular composition of structurally complex organic aerosols. The investigated aerosols were generated from the gas-phase ozonolysis of various C(10)H(16)-terpenes (alpha-pinene, beta-pinene, 3-carene, sabinene, limonene), and directly introduced into the ion source of the mass spectrometer. Negative ion chemical ionisation at atmospheric pressure (APCI(-)) enabled the detection of multifunctional carboxylic acid products by combining inherent sensitivity and molecular weight information. Sequential low-energy collision-induced product ion fragmentation experiments (MS(n)) were performed in order to elucidate characteristic decomposition pathways of the compounds. Dicarboxylic acids, oxocarboxylic acids and hydroxyketocarboxylic acid products could be clearly distinguished by multistage on-line MS. Furthermore, sabinonic acid and two C(9)-ether compounds were tentatively identified for the first time by applying on-line APCI(-)-MS(n). PMID:11746892

  16. TiO2-Coated Transparent Conductive Oxide (SnO2:F) Films Prepared by Atmospheric Pressure Chemical Vapor Deposition with High Durability against Atomic Hydrogen

    NASA Astrophysics Data System (ADS)

    Kambe, Mika; Sato, Kazuo; Kobayashi, Daisuke; Kurokawa, Yasuyoshi; Miyajima, Shinsuke; Fukawa, Makoto; Taneda, Naoki; Yamada, Akira; Konagai, Makoto

    2006-03-01

    The durability of textured transparent conductive oxide (TCO) thin films against atomic hydrogen was investigated. An ultrathin TiO2 layer of 2 nm thickness was deposited on textured fluorine-doped tin oxide (SnO2:F) films, successively by atmospheric pressure chemical vapor deposition (AP-CVD). TCO films with a TiO2 layer showed a higher optical transmittance and a lower resistivity after exposure to atomic hydrogen excited by very high frequency (VHF) plasma, while TCO films without a TiO2 layer showed a lower optical transmittance and a higher resistivity after the exposure. These TCO films were characterized by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS) before and after the exposure to atomic hydrogen.

  17. Uniform ZnO epitaxial films formed at atmospheric pressure by high-speed rotation-type mist chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Tanoue, Hironobu; Taniguchi, Takuya; Wada, Shohei; Yamamoto, Shinya; Nakamura, Shohei; Naka, Yoshihiro; Yoshikawa, Hiroyuki; Munekata, Mizue; Nagaoka, Shoji; Nakamura, Yusui

    2015-12-01

    Uniform ZnO epitaxial films were formed on 2-in.-diameter m-plane sapphire substrates by high-speed rotation-type mist chemical vapor deposition at atmospheric pressure, without using any vacuum equipment. The ZnO films were characterized by scanning electron microscopy, X-ray diffraction in θ-2θ and ϕ scanning modes, electron backscatter diffraction, and room-temperature photoluminescence measurements. Experimental results show that m-plane ZnO films were epitaxially grown on the m-plane sapphire substrates with high uniformity of not only thickness but also crystallinity and optical properties. These results will promote the progress of ZnO-based devices such as light-emitting diodes.

  18. An investigation into the optimum thickness of titanium dioxide thin films synthesized by using atmospheric pressure chemical vapour deposition for use in photocatalytic water oxidation.

    PubMed

    Hyett, Geoffrey; Darr, Jawwad A; Mills, Andrew; Parkin, Ivan P

    2010-09-10

    Twenty eight films of titanium dioxide of varying thickness were synthesised by using atmospheric pressure chemical vapour deposition (CVD) of titanium(IV) chloride and ethyl acetate onto glass and titanium substrates. Fixed reaction conditions at a substrate temperature of 660 °C were used for all depositions, with varying deposition times of 5-60 seconds used to control the thickness of the samples. A sacrificial electron acceptor system composed of alkaline sodium persulfate was used to determine the rate at which these films could photo-oxidise water in the presence of 365 nm light. The results of this work showed that the optimum thickness for CVD films on titanium substrates for the purposes of water oxidation was ≈200 nm, and that a platinum coating on the reverse of such samples leads to a five-fold increase in the observed rate of water oxidation. PMID:20645333

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

    SciTech Connect

    Ovchinnikova, Olga S; Van Berkel, Gary J

    2010-01-01

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

  20. Modified-Atmospheric Pressure-Matrix Assisted Laser Desorption/Ionization Identification of Friction Modifier Additives Oleamide and Ethoxylated Tallow Amines on Varied Metal Target Materials and Tribologically Stressed Steel Surfaces.

    PubMed

    Widder, Lukas; Ristic, Andjelka; Brenner, Florian; Brenner, Josef; Hutter, Herbert

    2015-11-17

    For many tasks in failure and damage analysis of surfaces deteriorated in heavy tribological contact, the detailed characterization of used lubricants and their additives is essential. The objective of the presented work is to establish accessibility of tribostressed surfaces for direct characterization via modified atmospheric pressure-matrix assisted laser desorption/ionization-mass spectrometry (m-AP-MALDI-MS). Special target holders were constructed to allow target samples of differing shape and form to fit into the desorption/ionization chamber. The best results of desorption and ionization on different target materials and varying roughnesses were achieved on smooth surfaces with low matrix/substrate interaction. M-AP-MALDI characterization of tribologically stressed steel surfaces after pin-on-disc sliding wear tests (SRV-tribotests) yielded positive identification of used friction modifier additives. Further structure elucidation by electrospray ionization mass spectrometry (ESI-MS) and measurements of worn surfaces by time-of-flight-secondary ion mass spectrometry (TOF-SIMS) accompanied findings about additive behavior and deterioration during tribological contact. Using m-AP-MALDI for direct offline examinations of worn surfaces may set up a quick method for determination of additives used for lubrication and general characterization of a tribological system. PMID:26491812

  1. Simultaneous determination of 16 brominated flame retardants in food and feed of animal origin by fast gas chromatography coupled to tandem mass spectrometry using atmospheric pressure chemical ionisation.

    PubMed

    Bichon, E; Guiffard, I; Vénisseau, A; Lesquin, E; Vaccher, V; Brosseaud, A; Marchand, P; Le Bizec, B

    2016-08-12

    A gas chromatography tandem mass spectrometry method using atmospheric pressure chemical ionisation was developed for the monitoring of 16 brominated flame retardants (7 usually monitored polybromodiphenylethers (PBDEs) and BDE #209 and 8 additional emerging and novel BFRs) in food and feed of animal origin. The developed analytical method has decreased the run time by three compared to conventional strategies, using a 2.5m column length (5% phenyl stationary phase, 0.1mm i.d., 0.1μmf.t.), a pulsed split injection (1:5) with carrier gas helium flow rate at 0.48mLmin(-1) in one run of 20 min. For most BFRs, analytical data were compared with the current analytical strategy relying on GC/EI/HRMS (double sector, R=10000 at 10% valley). Performances in terms of sensitivity were found to meet the Commission recommendation (118/2014/EC) for nBFRs. GC/APCI/MS/MS represents a promising alternative for multi-BFRs analysis in complex matrices, in that it allows the monitoring of a wider list of contaminants in a single injection and a shorter run time. PMID:27425757

  2. The analysis of beta-agonists by packed-column supercritical fluid chromatography with ultra-violet and atmospheric pressure chemical ionisation mass spectrometric detection.

    PubMed

    Jones, D C; Dost, K; Davidson, G; George, M W

    1999-06-01

    Packed-column supercritical fluid chromatography (pSFC) using ultra-violet (UV) and atmospheric pressure chemical ionisation (APCI) mass spectrometry (MS) provides a versatile method for the identification and quantification of beta-agonists. We have achieved good separation of clenbuterol, salbutamol, terbutaline and fenoterol with good resolution and reasonable retention times using a high concentration of methanol modifier in the supercritical CO2, together with small amounts of both acidic (trifluoroacetic acid, TFAA) and basic (triethylamine, TEA, or diethylamine, DEA) additives. APCI-MS gave unambiguous identification of the 4 analytes, and increasing cone voltage provided informative fragmentation patterns. The pSFC-MS technique was shown to be linear (R2 > or = 0.996) over the concentration range 1-50 micrograms ml-1. Single ion monitoring (SIM) gave detection limits (on-column) of 2.5 ng (clenbuterol), 0.83 ng (terbutaline), 7.6 ng (salbutamol) and 2.7 ng (fenoterol). The pSFC-MS system was shown to be reproducible within a day, between days, and between restrictors. Analysis of milk samples 'spiked' with beta-agonists showed that the matrix caused no interference, with detection limits of approximately 500 micrograms l-1 of beta-agonists. More dilute solutions could be analysed by pre-concentration before the SFC stage. PMID:10736867

  3. Novel chemical vapor deposition process of ZnO films using nonequilibrium N2 plasma generated near atmospheric pressure with small amount of O2 below 1%

    NASA Astrophysics Data System (ADS)

    Nose, Yukinori; Yoshimura, Takeshi; Ashida, Atsushi; Uehara, Tsuyoshi; Fujimura, Norifumi

    2016-05-01

    We propose a novel chemical vapor deposition (CVD) process of ZnO films involving a nonequilibrium N2 plasma generated near atmospheric pressure with small O2 concentration (O2%) below 1%. In the optical emission (OE) spectra of the plasma, OE lines corresponding to the NO-γ system ( A 2 Σ + → X 2 Πγ + ) were observed, despite the only introduced gases being N2 and O2; these vanish at an O2% of more than 1%. ZnO films were grown on a glass substrate placed in the plasma at a growth temperature of as low as 200 °C and at an O2% of below 1% in the presence of the NO-γ system. This plasma yielded almost the same growth rate for ZnO films as O2 plasma including atomic O radicals that are often observed in low-pressure O2 plasma, suggesting that some highly reactive oxidant was sufficiently generated in such a small O2%. ZnO films synthesized using this plasma exhibited excellent ( 0001 ) preferred orientation without other diffractions such as 10 1 ¯ 1 diffraction, and with an optical bandgap of 3.30 eV. Based on the analyses of the plasma and the exhaust gases, the coexistence state of NO-γ and O3 should be essential and useful for the decomposition and oxidation of Zn source material in the proposed CVD process.

  4. Organo-Chlorinated Thin Films Deposited by Atmospheric Pressure Plasma-Enhanced Chemical Vapor Deposition for Adhesion Enhancement between Rubber and Zinc-Plated Steel Monofilaments.

    PubMed

    Vandenabeele, Cédric; Bulou, Simon; Maurau, Rémy; Siffer, Frederic; Belmonte, Thierry; Choquet, Patrick

    2015-07-01

    A continuous-flow plasma process working at atmospheric pressure is developed to enhance the adhesion between a rubber compound and a zinc-plated steel monofilament, with the long-term objective to find a potential alternative to the electrolytic brass plating process, which is currently used in tire industry. For this purpose, a highly efficient tubular dielectric barrier discharge reactor is built to allow the continuous treatment of "endless" cylindrical substrates. The best treatment conditions found regarding adhesion are Ar/O2 plasma pretreatment, followed by the deposition from dichloromethane of a 75 nm-thick organo-chlorinated plasma polymerized thin film. Ar/O2 pretreatment allows the removal of organic residues, coming from drawing lubricants, and induces external growth of zinc oxide. The plasma layer has to be preferably deposited at low power to conserve sufficient hydrocarbon moieties. Surface analyses reveal the complex chemical mechanism behind the establishment of strong adhesion levels, more than five times higher after the plasma treatment. During the vulcanization step, superficial ZnO reacts with the chlorinated species of the thin film and is converted into porous and granular bump-shaped ZnwOxHyClz nanostructures. Together, rubber additives diffuse through the plasma layer and lead to the formation of zinc sulfide on the substrate surface. Hence, two distinct interfaces, rubber/thin film and thin film/substrate, are established. On the basis of these observations, hypotheses explaining the high bonding strength results are formulated. PMID:26069994

  5. Structural Characterization of Polycrystalline 3C-SiC Films Prepared at High Rates by Atmospheric Pressure Plasma Chemical Vapor Deposition Using Monomethylsilane

    NASA Astrophysics Data System (ADS)

    Kakiuchi, Hiroaki; Ohmi, Hiromasa; Nakamura, Ryota; Aketa, Masatoshi; Yasutake, Kiyoshi

    2006-10-01

    Polycrystalline cubic silicon carbide (3C-SiC) films were deposited at a relatively low temperature of 1070 K on Si(001) substrates by atmospheric pressure plasma chemical vapor deposition. Monomethylsilane (CH3SiH3) was used as the single source. CH4 and SiH4 dual sources were also used to compare deposition characteristics. Under the present deposition conditions, very high deposition rates of more than 3 nm/s were obtained. The structure of the SiC films was evaluated by reflection high-energy electron diffraction, Fourier transform infrared absorption spectroscopy and cross-sectional transmission electron microscopy. In addition, optical emission spectroscopy was employed to study the chemical reactions in the CH4/SiH4 and CH3SiH3 plasmas. The results showed that increasing H2 concentration is essential in forming a high quality 3C-SiC film by enhancing the hydrogen elimination reaction at the film-growing surface. From the optical emission spectra, it was found that atomic hydrogen generated by adding H2 in the plasma increase the amount of principal precursors for the film growth. The utilization of CH3SiH3 also led to a higher concentration of principal precursors in the plasma, enhancing the incorporation of Si-C bonds into the film. As a consequence of simultaneously using a high H2 concentration and the CH3SiH3 single source, the columnar growth of 3C-SiC crystallites was achieved.

  6. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer

    NASA Astrophysics Data System (ADS)

    Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth

    2016-08-01

    In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs.

  7. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer.

    PubMed

    Hoegg, Edward D; Barinaga, Charles J; Hager, George J; Hart, Garret L; Koppenaal, David W; Marcus, R Kenneth

    2016-08-01

    In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs. Graphical Abstract ᅟ. PMID:27080006

  8. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer

    NASA Astrophysics Data System (ADS)

    Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth

    2016-04-01

    In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs.

  9. Determination of hexabromocyclododecane by flowing atmospheric pressure afterglow mass spectrometry.

    PubMed

    Smoluch, Marek; Silberring, Jerzy; Reszke, Edward; Kuc, Joanna; Grochowalski, Adam

    2014-10-01

    The first application of a flowing atmospheric-pressure afterglow ion source for mass spectrometry (FAPA-MS) for the chemical characterization and determination of hexabromocyclododecane (HBCD) is presented. The samples of technical HBCD and expanded polystyrene foam (EPS) containing HBCD as a flame retardant were prepared by dissolving the appropriate solids in dichloromethane. The ionization of HBCD was achieved with a prototype FAPA source. The ions were detected in the negative-ion mode. The ions corresponding to a deprotonated HBCD species (m/z 640.7) as well as chlorine (m/z 676.8), nitrite (m/z 687.8) and nitric (m/z 703.8) adducts were observed in the spectra. The observed isotope pattern is characteristic for a compound containing six bromine atoms. This technique is an effective approach to detect HBCD, which is efficiently ionized in a liquid phase, resulting in high detection efficiency and sensitivity. PMID:25059130

  10. Comparing Laser Desorption Ionization and Atmospheric Pressure Photoionization Coupled to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry To Characterize Shale Oils at the Molecular Level

    USGS Publications Warehouse

    Cho, Yunjo; Jin, Jang Mi; Witt, Matthias; Birdwell, Justin E.; Na, Jeong-Geol; Roh, Nam-Sun; Kim, Sunghwan

    2013-01-01

    Laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to analyze shale oils. Previous work showed that LDI is a sensitive ionization technique for assessing aromatic nitrogen compounds, and oils generated from Green River Formation oil shales are well-documented as being rich in nitrogen. The data presented here demonstrate that LDI is effective in ionizing high-double-bond-equivalent (DBE) compounds and, therefore, is a suitable method for characterizing compounds with condensed structures. Additionally, LDI generates radical cations and protonated ions concurrently, the distribution of which depends upon the molecular structures and elemental compositions, and the basicity of compounds is closely related to the generation of protonated ions. This study demonstrates that LDI FT-ICR MS is an effective ionization technique for use in the study of shale oils at the molecular level. To the best of our knowledge, this is the first time that LDI FT-ICR MS has been applied to shale oils.

  11. Coupling laser ablation/desorption electrospray ionization to atmospheric pressure drift tube ion mobility spectrometry for the screening of antimalarial drug quality.

    PubMed

    Harris, Glenn A; Graf, Stephan; Knochenmuss, Richard; Fernández, Facundo M

    2012-07-01

    Significant developments in the field of ambient desorption/ionization mass spectrometry (MS) have led to high-throughput direct analysis and imaging capabilities. However, advances in coupling ambient ionization techniques with standalone drift tube ion mobility spectrometry (DTIMS) have been comparatively slower, despite the attractive ruggedness and simplicity of IMS. In this study, we have developed and characterized a laser ablation/desorption electrospray ionization (LADESI) DTIMS platform, and applied it to the detection of active pharmaceutical ingredients (APIs) in antimalarial tablets collected in developing countries. The overarching goal of this work was to perform an initial evaluation of LADESI DTIMS as a technique with the potential for constituting the core of a portable drug quality-testing platform. The set-up consisted of an IR laser for desorption and an electrospray ionizer for capturing the ablated plume coupled to a high-resolution monolithic resistive glass drift tube ion mobility spectrometer. For more confident API identification, tablet extracts were also investigated via electrospray IM MS to correlate LADESI DTIMS reduced mobility (K(0)) values to m/z values. Overall, it was found that the IR LADESI DTIMS platform provided distinct ion mobility spectral fingerprints that could be used to detect the presence of the expected APIs, helping to distinguish counterfeit drugs from their genuine counterparts. PMID:22606690

  12. A dilute Cu(Ni) alloy for synthesis of large-area Bernal stacked bilayer graphene using atmospheric pressure chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Madito, M. J.; Bello, A.; Dangbegnon, J. K.; Oliphant, C. J.; Jordaan, W. A.; Momodu, D. Y.; Masikhwa, T. M.; Barzegar, F.; Fabiane, M.; Manyala, N.

    2016-01-01

    A bilayer graphene film obtained on copper (Cu) foil is known to have a significant fraction of non-Bernal (AB) stacking and on copper/nickel (Cu/Ni) thin films is known to grow over a large-area with AB stacking. In this study, annealed Cu foils for graphene growth were doped with small concentrations of Ni to obtain dilute Cu(Ni) alloys in which the hydrocarbon decomposition rate of Cu will be enhanced by Ni during synthesis of large-area AB-stacked bilayer graphene using atmospheric pressure chemical vapour deposition. The Ni doped concentration and the Ni homogeneous distribution in Cu foil were confirmed with inductively coupled plasma optical emission spectrometry and proton-induced X-ray emission. An electron backscatter diffraction map showed that Cu foils have a single (001) surface orientation which leads to a uniform growth rate on Cu surface in early stages of graphene growth and also leads to a uniform Ni surface concentration distribution through segregation kinetics. The increase in Ni surface concentration in foils was investigated with time-of-flight secondary ion mass spectrometry. The quality of graphene, the number of graphene layers, and the layers stacking order in synthesized bilayer graphene films were confirmed by Raman and electron diffraction measurements. A four point probe station was used to measure the sheet resistance of graphene films. As compared to Cu foil, the prepared dilute Cu(Ni) alloy demonstrated the good capability of growing large-area AB-stacked bilayer graphene film by increasing Ni content in Cu surface layer.

  13. Nanocapillary Atmospheric Pressure Plasma Jet: A Tool for Ultrafine Maskless Surface Modification at Atmospheric Pressure.

    PubMed

    Motrescu, Iuliana; Nagatsu, Masaaki

    2016-05-18

    With respect to microsized surface functionalization techniques we proposed the use of a maskless, versatile, simple tool, represented by a nano- or microcapillary atmospheric pressure plasma jet for producing microsized controlled etching, chemical vapor deposition, and chemical modification patterns on polymeric surfaces. In this work we show the possibility of size-controlled surface amination, and we discuss it as a function of different processing parameters. Moreover, we prove the successful connection of labeled sugar chains on the functionalized microscale patterns, indicating the possibility to use ultrafine capillary atmospheric pressure plasma jets as versatile tools for biosensing, tissue engineering, and related biomedical applications. PMID:27116255

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

    NASA Astrophysics Data System (ADS)

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

    2010-02-01

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

  15. Large area atmospheric-pressure plasma jet

    DOEpatents

    Selwyn, Gary S.; Henins, Ivars; Babayan, Steve E.; Hicks, Robert F.

    2001-01-01

    Large area atmospheric-pressure plasma jet. A plasma discharge that can be operated at atmospheric pressure and near room temperature using 13.56 MHz rf power is described. Unlike plasma torches, the discharge produces a gas-phase effluent no hotter than 250.degree. C. at an applied power of about 300 W, and shows distinct non-thermal characteristics. In the simplest design, two planar, parallel electrodes are employed to generate a plasma in the volume therebetween. A "jet" of long-lived metastable and reactive species that are capable of rapidly cleaning or etching metals and other materials is generated which extends up to 8 in. beyond the open end of the electrodes. Films and coatings may also be removed by these species. Arcing is prevented in the apparatus by using gas mixtures containing He, which limits ionization, by using high flow velocities, and by properly spacing the rf-powered electrode. Because of the atmospheric pressure operation, there is a negligible density of ions surviving for a sufficiently long distance beyond the active plasma discharge to bombard a workpiece, unlike the situation for low-pressure plasma sources and conventional plasma processing methods.

  16. Quantitative determination of dexamethasone in bovine milk by liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Cherlet, Marc; De Baere, Siegrid; De Backer, Patrick

    2004-06-01

    Dexamethasone (DXM) is a synthetic glucocorticoid that is authorized for therapeutic use in veterinary medicine. The European Community (EC) fixed a maximum residue limit (MRL) at 2ng/g for liver, 0.75ng/g for muscle and kidney tissues, and 0.3ng/ml for milk, while its use as growth-promoter is completely banned. The purpose of this study was to develop and validate a simple and reliable method to determine DXM residues in bovine milk. Milk proteins were removed by the addition of concentrated trichloroacetic acid and paper filtration. Solid-phase extraction clean-up on a C18 reversed phase column was performed to obtain an extract suitable for liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. Chromatographic separation of DXM and the internal standard desoximetasone, was achieved on a PLRP-S polymeric reversed phase column, using a mixture of 0.1% (v/v) acetic acid in water (mobile phase A) and acetonitrile (mobile phase B) as the mobile phases. They were identified using the MS/MS detection technique, and were subsequently quantified. The method has been validated according to the requirements of the EC at 0.15, 0.30 and 0.60ng/ml (being half the MRL, the MRL and double the MRL levels fixed by the EC). Calibration graphs were prepared in the 0.15-5ng/ml range and good linearity was achieved (r>or=0.99 and goodness of fit

  17. On-Chip Solid-Phase Extraction Preconcentration/Focusing Substrates Coupled to Atmospheric Pressure Matrix-Assisted Laser Desorption/Ionization Ion Trap Mass Spectrometry for High Sensitivity Biomolecule Analysis

    PubMed Central

    Navare, Arti; Nouzova, Marcela; Noriega, Fernando G.; Hernández-Martínez, Salvador; Menzel, Christoph; Fernández, Facundo M.

    2009-01-01

    Atmospheric pressure matrix-assisted laser desorption/ionization (AP-MALDI) has proven a convenient and rapid method for ion production in the mass spectrometric analysis of biomolecules. AP-MALDI and electrospray ion sources are easily interchangeable in most mass spectrometers. However, AP-MALDI suffers from less-than-optimal sensitivity due to ion losses during transport from the atmosphere into the vacuum of the mass spectrometer. Here, we study the signal-to-noise (S/N) ratio gains observed when an on-chip dynamic preconcentration/focusing approach is coupled to AP-MALDI for the MS analysis of neuropeptides and protein digests. It was found that, in comparison with conventional AP-MALDI targets, focusing targets showed (1) a sensitivity enhancement of approximately two orders of magnitude with S/N gains of 200–900 for hydrophobic substrates, and 150–400 for weak cation exchange (WCX) substrates; (2) improved detection limits as low as 5 fmol/μL for standard peptides; (3) significantly reduced matrix background; and (4) higher inter-day reproducibility. The improved sensitivity allowed successful tandem MS sequencing of dilute solutions of a derivatized tryptic digest of a protein standard, and enabled the first reported AP-MALDI MS detection of neuropeptides from Aedes aegypti mosquito heads. PMID:19140128

  18. Special issue: diagnostics of atmospheric pressure microplasmas

    NASA Astrophysics Data System (ADS)

    Bruggeman, Peter; Czarnetzki, Uwe; Tachibana, Kunihide

    2013-11-01

    In recent decades, a strong revival of non-equilibrium atmospheric pressure plasma studies has developed in the form of microplasmas. Microplasmas have typical scales of 1 mm or less and offer a very exciting research direction in the field of plasma science and technology as the discharge physics can be considerably different due to high collisionality and the importance of plasma-surface interaction. These high-pressure small-scale plasmas have a diverse range of physical and chemical properties. This diversity coincides with various applications including light/UV sources [1], material processing [2], chemical analysis [3], material synthesis [4], electromagnetics [5], combustion [6] and even medicine [7]. At atmospheric pressure, large scale plasmas have the tendency to become unstable due to the high collision rates leading to enhanced heating and ionization compared to their low-pressure counterparts. As low-pressure plasmas typically operate in reactors with sizes of tens of centimetres, scaling up the pressure to atmospheric pressure the size of the plasma reduces to typical sizes below 1 mm. A natural approach of stabilizing atmospheric pressure plasmas is thus the use of microelectrode geometries. Traditionally microplasmas have been produced in confined geometries which allow one to stabilize dc excited discharges. This stabilization is intrinsically connected to the large surface-to-volume ratio which enhances heat transfer and losses of charged and excited species to the walls. Currently challenging boundaries are pushed by producing microcavity geometries with dimensions of the order of 1 µm [8]. The subject of this special issue, diagnostics of microplasmas, is motivated by the many challenges in microplasma diagnostics in view of the complex chemistry and strong spatial (and even temporal) gradients of species densities and plasma properties. Atmospheric pressure plasmas have a very long history dating back more than 100 years, with early work of

  19. Mass spectrometry of atmospheric pressure plasmas

    NASA Astrophysics Data System (ADS)

    Große-Kreul, S.; Hübner, S.; Schneider, S.; Ellerweg, D.; von Keudell, A.; Matejčík, S.; Benedikt, J.

    2015-08-01

    Atmospheric pressure non-equilibrium plasmas (APPs) are effective source of radicals, metastables and a variety of ions and photons, ranging into the vacuum UV spectral region. A detailed study of these species is important to understand and tune desired effects during the interaction of APPs with solid or liquid materials in industrial or medical applications. In this contribution, the opportunities and challenges of mass spectrometry for detection of neutrals and ions from APPs, fundamental physical phenomena related to the sampling process and their impact on the measured densities of neutrals and fluxes of ions, will be discussed. It is shown that the measurement of stable neutrals and radicals requires a proper experimental design to reduce the beam-to-background ratio, to have little beam distortion during expansion into vacuum and to carefully set the electron energy in the ionizer to avoid radical formation through dissociative ionization. The measured ion composition depends sensitively on the degree of impurities present in the feed gas as well as on the setting of the ion optics used for extraction of ions from the expanding neutral-ion mixture. The determination of the ion energy is presented as a method to show that the analyzed ions are originating from the atmospheric pressure plasma.

  20. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    DOE PAGESBeta

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-04-05

    Here, benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combinationmore » of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

  1. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-04-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt-1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion-molecule reactions likely proceed through a combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.

  2. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kim, M. J.; Zoerb, M. C.; Campbell, N. R.; Zimmermann, K. J.; Blomquist, B. W.; Huebert, B. J.; Bertram, T. H.

    2015-10-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e. DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt-1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a weaker electric field, demonstrated that ion-molecule reactions likely proceed through a combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer. Measurements from the two instruments were highly correlated (R2=0.80) over a wide range of sampling conditions.

  3. Microwave Atmospheric-Pressure Sensor

    NASA Technical Reports Server (NTRS)

    Flower, D. A.; Peckham, G. E.; Bradford, W. J.

    1986-01-01

    Report describes tests of microwave pressure sounder (MPS) for use in satellite measurements of atmospheric pressure. MPS is multifrequency radar operating between 25 and 80 GHz. Determines signal absorption over vertical path through atmosphere by measuring strength of echoes from ocean surface. MPS operates with cloud cover, and suitable for use on current meteorological satellites.

  4. Phospholipid Topography of Whole-Body Sections of the Anopheles stephensi Mosquito, Characterized by High-Resolution Atmospheric-Pressure Scanning Microprobe Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Imaging.

    PubMed

    Khalil, Saleh M; Römpp, Andreas; Pretzel, Jette; Becker, Katja; Spengler, Bernhard

    2015-11-17

    High-resolution atmospheric-pressure scanning microprobe matrix-assisted laser desorption/ionization mass spectrometry imaging (AP-SMALDI MSI) has been employed to study the molecular anatomical structure of rodent malaria vector Anopheles stephensi mosquitoes. A dedicated sample preparation method was developed which suits both, the special tissue properties of the sample and the requirements of high-resolution MALDI imaging. Embedding in 5% carboxymethylcellulose (CMC) was used to maintain the tissue integrity of the whole mosquitoes, being very soft, fragile, and difficult to handle. Individual lipid compounds, specifically representing certain cell types, tissue areas, or organs, were detected and imaged in 20 μm-thick whole-body tissue sections at a spatial resolution of 12 μm per image pixel. Mass spectrometric data and information quality were based on a mass resolution of 70,000 (at m/z 200) and a mass accuracy of better than 2 ppm in positive-ion mode on an orbital trapping mass spectrometer. A total of 67 imaged lipids were assigned by database search and, in a number of cases, identified via additional MS/MS fragmentation studies directly from tissue. This is the first MSI study at 12 μm spatial resolution of the malaria vector Anopheles. The study provides insights into the molecular anatomy of Anopheles stephensi and the distribution and localization of major classes of glycerophospholipids and sphingolipids. These data can be a basis for future experiments, investigating, e.g., the metabolism of Plasmodium-infected and -uninfected Anopheles mosquitoes. PMID:26491885

  5. Real-time monitoring of in situ gas-phase H/D exchange reactions of cations by atmospheric pressure helium plasma ionization mass spectrometry (HePI-MS).

    PubMed

    Attygalle, Athula B; Gangam, Rekha; Pavlov, Julius

    2014-01-01

    An enclosed atmospheric-pressure helium-plasma ionization (HePI-MS) source avoids, or minimizes, undesired back-exchange reactions usually encountered during deuterium incorporation experiments under ambient-pressure open-source conditions. A simple adaptation of an ESI source provides an economical way of conducting gas phase hydrogen/deuterium (H/D) exchange reactions (HDX) in real time without the need for complicated hardware modifications. For example, the spectrum of [(2)H8]toluene recorded under exposed ambient conditions showed the base peak at m/z 96 due to fast leaching of ring hydrogens because of interactions with H2O vapor present in the open source. Such D/H exchanges are rapidly reversed if the deuterium-depleted [(2)H8]toluene is exposed to D2O vapor. In addition to the enumeration of labile protons, our procedure enables the identification of protonation sites in molecules unambiguously, by the number of H/D exchanges observed in real time. For example, molecules such as tetrahydrofuran and pyridine protonate at the heteroatom and consequently undergo only one H/D exchange, whereas ethylbenzene, which protonates at a ring position of the aromatic ring, undergoes six H/D exchanges. In addition, carbocations generated in situ by in-source fragmentation of precursor protonated species, such as benzyl alcohol, do not undergo any rapid H/D exchanges. Because radical cations, second-generation cations (ions formed by losing a small molecule from a precursor ion), or those formed by hydride abstraction do not undergo rapid H/D exchanges, our technique provides a way to distinguish these ions from protonated molecules. PMID:24325360

  6. 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.

  7. When API Mass Spectrometry Meets Super Atmospheric Pressure Ion Sources.

    PubMed

    Chen, Lee Chuin

    2015-01-01

    In a tutorial paper on the application of free-jet technique for API-MS, John Fenn mentioned that "…for a number of years and a number of reasons, it has been found advantageous in many situations to carry out the ionization process in gas at pressures up to 1000 Torr or more" (Int. J. Mass Spectrom. 200: 459-478, 2000). In fact, the first ESI mass spectrometer constructed by Yamashita and Fenn had a counter-flow curtain gas source at 1050 Torr (ca. 1.4 atm) to sweep away the neutral (J. Phys. Chem. 88: 4451-4459, 1984). For gaseous ionization using electrospray plume, theoretical analysis also shows that "super-atmospheric operation would be more preferable in space-charge-limited situations."(Int. J. Mass Spectrom. 300: 182-193, 2011). However, electrospray and the corona-based chemical ion source (APCI) in most commercial instrument are basically operated under an atmospheric pressure ambient, perhaps out of the concern of safety, convenience and simplicity in maintenance. Running the ion source at pressure much higher than 1 atm is not so common, but had been done by a number of groups as well as in our laboratory. A brief review on these ion sources will be given in this paper. PMID:26819912

  8. When API Mass Spectrometry Meets Super Atmospheric Pressure Ion Sources

    PubMed Central

    Chen, Lee Chuin

    2015-01-01

    In a tutorial paper on the application of free-jet technique for API-MS, John Fenn mentioned that “…for a number of years and a number of reasons, it has been found advantageous in many situations to carry out the ionization process in gas at pressures up to 1000 Torr or more” (Int. J. Mass Spectrom. 200: 459–478, 2000). In fact, the first ESI mass spectrometer constructed by Yamashita and Fenn had a counter-flow curtain gas source at 1050 Torr (ca. 1.4 atm) to sweep away the neutral (J. Phys. Chem. 88: 4451–4459, 1984). For gaseous ionization using electrospray plume, theoretical analysis also shows that “super-atmospheric operation would be more preferable in space-charge-limited situations.”(Int. J. Mass Spectrom. 300: 182–193, 2011). However, electrospray and the corona-based chemical ion source (APCI) in most commercial instrument are basically operated under an atmospheric pressure ambient, perhaps out of the concern of safety, convenience and simplicity in maintenance. Running the ion source at pressure much higher than 1 atm is not so common, but had been done by a number of groups as well as in our laboratory. A brief review on these ion sources will be given in this paper. PMID:26819912

  9. Atmospheric pressure ion focusing with a vortex stream.

    PubMed

    Kolomiets, Yuri N; Pervukhin, Viktor V

    2011-09-30

    For successful operation of ionization analysis techniques an efficient sampling and sample ion transportation into an analytical path are required. This is of particular importance for atmospheric pressure ionization sources like corona discharge, electrospray, MALDI, ionization with radioactive isotopes ((3)H, (63)Ni) that produce nonuniform spatial distribution of sample ions. The available methods of sample ion focusing with electric fields are either efficient at reduced pressure (to 1 Torr) or feature high sample losses. In this paper we suggest to use a highly whirled gas stream for atmospheric pressure ion focusing. We use a (63)Ni radioactive source to produce an ionized bipolar sample at atmospheric pressure. It is shown by experiments that compared to an aspiration method a forced highly whirled vortex stream allows one to enhance the efficiency of remote ionized sample collection at distances equal to the vortex sampler diameter by an order of magnitude. With a vortex stream, a sixfold increase in the efficiency of the radial ionized sample collection has been obtained. It may be deduced that with the vortex stream remote sampling obtains a new feature which is characterized by a considerable enhancement of the efficiency of the ionized sample collection and can be called as a "gas-dynamic" ionized sample focusing. Considered is the effect of recombination losses of the ionized sample during the remote sampling thereof with the vortex sampler. Prospects for a practical implementation of the vortex sampler for solving the problems of the customs control over the smuggling of radioactive α and β sources are made based on the research results. PMID:21872021

  10. The Performance Improvement of N2 Plasma Treatment on ZrO2 Gate Dielectric Thin-Film Transistors with Atmospheric Pressure Plasma-Enhanced Chemical Vapor Deposition IGZO Channel.

    PubMed

    Wu, Chien-Hung; Huang, Bo-Wen; Chang, Kow-Ming; Wang, Shui-Jinn; Lin, Jian-Hong; Hsu, Jui-Mei

    2016-06-01

    The aim of this paper is to illustrate the N2 plasma treatment for high-κ ZrO2 gate dielectric stack (30 nm) with indium-gallium-zinc-oxide (IGZO) thin-film transistors (TFTs). Experimental results reveal that a suitable incorporation of nitrogen atoms could enhance the device performance by eliminating the oxygen vacancies and provide an amorphous surface with better surface roughness. With N2 plasma treated ZrO2 gate, IGZO channel is fabricated by atmospheric pressure plasma-enhanced chemical vapor deposition (AP-PECVD) technique. The best performance of the AP-PECVD IGZO TFTs are obtained with 20 W-90 sec N2 plasma treatment with field-effect mobility (μ(FET)) of 22.5 cm2/V-s, subthreshold swing (SS) of 155 mV/dec, and on/off current ratio (I(on)/I(off)) of 1.49 x 10(7). PMID:27427669

  11. 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.

  12. Domestic atmospheric pressure thermal deaerators

    NASA Astrophysics Data System (ADS)

    Egorov, P. V.; Gimmelberg, A. S.; Mikhailov, V. G.; Baeva, A. N.; Chuprakov, M. V.; Grigoriev, G. V.

    2016-04-01

    Based on many years of experience and proven technical solutions, modern atmospheric pressure deaerators of the capacity of 0.4 to 800 t/h were designed and developed. The construction of such deaerators is based on known and explored technical solutions. A two-stage deaeration scheme is applied where the first stage is a jet dripping level (in a column) and the second one is a bubble level (in a tank). In the design of deaeration columns, low-pressure hydraulic nozzles (Δ p < 0.15 MPa) and jet trays are used, and in deaerator tank, a developed "flooded" sparger is applied, which allows to significantly increase the intensity of the heat and mass exchange processes in the apparatus. The use of the two efficient stages in a column and a "flooded" sparger in a tank allows to reliably guarantee the necessary water heating and deaeration. Steam or "superheated" water of the temperature of t ≥ 125°C can be used as the coolant in the deaerators. The commissioning tests of the new deaerator prototypes of the capacity of 800 and 500 t/h in the HPP conditions showed their sustainable, reliable, and efficient work in the designed range of hydraulic and thermal loads. The content of solved oxygen and free carbon dioxide in make-up water after deaerators meets the requirements of State Standard GOST 16860-88, the operating rules and regulations, and the customer's specifications. Based on these results, the proposals were developed on the structure and the design of deaerators of the productivity of more than 800 t/h for the use in circuits of large heating systems and the preparation of feed water to the TPP at heating and industrial-heating plants. The atmospheric pressure thermal deaerators developed at NPO TsKTI with consideration of the current requirements are recommended for the use in water preparation schemes of various power facilities.

  13. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    DOE PAGESBeta

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-01-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combination of ligand-switching and directmore » charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

  14. GC/MS on an LC/MS instrument using atmospheric pressure photoionization

    NASA Astrophysics Data System (ADS)

    McEwen, Charles N.

    2007-01-01

    Atmospheric pressure (AP) GC/MS was first introduced by Horning et al. [E.C. Horning, M.G. Horning, D.I. Carroll, I. Dzidic, R.N. Stillwell, Anal. Chem. 45 (1973) 936] using 63Ni as a beta-emitter for ionization. Because, at the time special instrumentation was required, the technique was only applied with consistency to negative ion environmental studies where high sensitivity was required [T. Kinouchi, A.T.L. Miranda, L.G. Rushing, F.A. Beland, W.A. Korfmacher, J. High Resolut. Chromatogr., Chromatogr. Commun. 13 (1990) 281]. Currently, AP ion sources are commonly available on LC/MS instruments and recently a method was reported for converting an AP-LC/MS ion source to a combination AP-LC/MS:GC/MS source [C.N. McEwen, R.G. McKay, J. Am. Soc. Mass Spectrom. 16 (2005) 1730]. Here, we report the use of atmospheric pressure photoionization (APPI) with GC/MS and compare this to AP chemical ionization (APCI) GC/MS and electron ionization (EI) GC/MS. Using a nitrogen purge gas, we observe excellent chromatographic resolution and abundant molecular M+ and MH+ ions as well as structurally significant fragment ions. Comparison of a 9.8 eV UV lamp with a 10.6 eV lamp, as expected, shows that the higher energy lamp gives more universal ionization and more fragment ions than the lower energy lamp. While there are clear differences in the fragment ions observed by APPI-MS versus EI-MS, there are also similarities. As might be expected from the ionization mechanism, APPI ionization is similar to low energy EI. These odd electron fragment ions are useful in identifying unknown compounds by comparison to mass spectra in computer libraries.

  15. Infrared laser ablation atmospheric pressure photoionization mass spectrometry.

    PubMed

    Vaikkinen, Anu; Shrestha, Bindesh; Kauppila, Tiina J; Vertes, Akos; Kostiainen, Risto

    2012-02-01

    In this paper we introduce laser ablation atmospheric pressure photoionization (LAAPPI), a novel atmospheric pressure ion source for mass spectrometry. In LAAPPI the analytes are ablated from water-rich solid samples or from aqueous solutions with an infrared (IR) laser running at 2.94 μm wavelength. Approximately 12 mm above the sample surface, the ablation plume is intercepted with an orthogonal hot solvent (e.g., toluene or anisole) jet, which is generated by a heated nebulizer microchip and directed toward the mass spectrometer inlet. The ablated analytes are desolvated and ionized in the gas-phase by atmospheric pressure photoionization using a 10 eV vacuum ultraviolet krypton discharge lamp. The effect of operational parameters and spray solvent on the performance of LAAPPI is studied. LAAPPI offers ~300 μm lateral resolution comparable to, e.g., matrix-assisted laser desorption ionization. In addition to polar compounds, LAAPPI efficiently ionizes neutral and nonpolar compounds. The bioanalytical application of the method is demonstrated by the direct LAAPPI analysis of rat brain tissue sections and sour orange (Citrus aurantium) leaves. PMID:22242626

  16. Gas flow dependence of atmospheric pressure plasma needle discharge characteristics

    NASA Astrophysics Data System (ADS)

    Qian, Muyang; Yang, Congying; Liu, Sanqiu; Chen, Xiaochang; Ni, Gengsong; Wang, Dezhen

    2016-04-01

    In this paper, a two-dimensional coupled model of neutral gas flow and plasma dynamics is presented to explain the gas flow dependence of discharge characteristics in helium plasma needle at atmospherics pressure. The diffusional mixing layer between the helium jet core and the ambient air has a moderate effect on the streamer propagation. The obtained simulation results present that the streamer shows the ring-shaped emission profile at a moderate gas flow rate. The key chemical reactions which drive the streamer propagation are electron-impact ionization of helium neutral, nitrogen and oxygen molecules. At a moderate gas flow rate of 0.5 slm, a significant increase in propagation velocity of the streamer is observed due to appropriate quantity of impurities air diffuse into the helium. Besides, when the gas flow rate is below 0.35 slm, the radial density of ground-state atomic oxygen peaks along the axis of symmetry. However, when the gas flow rate is above 0.5 slm, a ring-shaped density distribution appears. The peak density is on the order of 1020 m-3 at 10 ns in our work.

  17. Simultaneous determination of volatile and non-volatile nitrosamines in processed meat products by liquid chromatography tandem mass spectrometry using atmospheric pressure chemical ionisation and electrospray ionisation.

    PubMed

    Herrmann, S S; Duedahl-Olesen, L; Granby, K

    2014-02-21

    A sensitive, selective and generic method has been developed for the simultaneous determination of the contents (μgkg(-1) range) of both volatile nitrosamines (VNA) and non-volatile nitrosamines (NVNA) in processed meat products. The extraction procedure only requires basic laboratory equipment and a small volume of organic solvent. Separation and quantification were performed by the developed LC-(APCI/ESI)MS/MS method. The method was validated using spiked samples of three different processed meat products. Satisfactory recoveries (50-130%) and precisions (2-23%) were obtained for eight VNA and six NVNAs with LODs generally between 0.2 and 1μgkg(-1), though for a few analyte/matrix combinations higher LODs were obtained (3 to 18μgkg(-1)). The validation results show that results obtained for one meat product is not always valid for other meat products. We were not able to obtain satisfactory results for N-nitrosohydroxyproline (NHPRO), N-nitrosodibenzylamine (NDBzA) and N-nitrosodiphenylamine (NDPhA). Application of the APCI interface improved the sensitivity of the method, because of less matrix interference, and gave the method a wider scope, as some NAs were ionisable only by APCI. However, it was only possible to ionize N-nitroso-thiazolidine-4-carboxylic acid (NTCA) and N-nitroso-2-methyl-thiazolidine-4-carboxylic acid (NMTCA) by ESI. The validated method was applied for the analysis of processed meat products and contents of N-nitrosodimethylamine (NDMA), N-nitrosopyrrolidine (NPYR), N-nitrosomethylaniline (NMA), N-nitrosoproline (NPRO), NTCA, and NMTCA were found in one or several nitrite cured meat products, whereas none were detected in non-nitrite cured bacon. PMID:24468241

  18. Development of a combinatorial atmospheric pressure cold plasma processor

    NASA Astrophysics Data System (ADS)

    Terajima, Takeshi; Koinuma, Hideomi

    2004-02-01

    Low-temperature plasma can be generated under atmospheric pressure by applying an RF (13.56 MHz) voltage between parallel electrodes, the surfaces of which are preferably covered with an insulator. Applications of this atmospheric pressure cold plasma include thin film deposition, chemical synthesis, etching, resist-ashing, surface treatment, and sterilization. For seeking further improvement of the system and more applications, we have developed a combinatorial atmospheric pressure cold plasma generator to fabricate composition spread thin films by synchronizing the variation of feeding gas ratio with the substrate stage motion. This system can be extended to fabricating a variety of combinatorial libraries by controlling other parameters in the operation such as the gas flow rate, the RF power, substrate temperature, and the treatment time. The utility of this combinatorial plasma process has been demonstrated with the plasma copolymerization of CO 2 with ethylene to fix CO 2 into the plasma polymerized film in the form of ester linkage.

  19. Spacecraft Sterilization Using Non-Equilibrium Atmospheric Pressure Plasma

    NASA Technical Reports Server (NTRS)

    Cooper, Moogega; Vaze, Nachiket; Anderson, Shawn; Fridman, Gregory; Vasilets, Victor N.; Gutsol, Alexander; Tsapin, Alexander; Fridman, Alexander

    2007-01-01

    As a solution to chemically and thermally destructive sterilization methods currently used for spacecraft, non-equilibrium atmospheric pressure plasmas are used to treat surfaces inoculated with Bacillus subtilis and Deinococcus radiodurans. Evidence of significant morphological changes and reduction in viability due to plasma exposure will be presented, including a 4-log reduction of B. subtilis after 2 minutes of dielectric barrier discharge treatment.

  20. [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

  1. Transport Properties of CrO2 (100) Film Grown on TiO2 by a Simple Atmosphere Pressure Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Xie, Liang; Zhang, Jin Zhi; Cui, Nai Yi; Zhang, Hong Guang

    2014-06-01

    Epitaxial CrO2 (100)-oriented film was successfully fabricated on TiO2 (100) substrate by a simple chemical vapor deposition in a two-zone furnace with oxygen flow from a CrO3 precursor. The transport measurements show that the CrO2 film is metallic with a small residual resistivity 4 μΩ cm down to 0.6 K. The temperature dependence of resistivity was best described by a phenomenological expression ρ(T) = ρ0 + AT2exp(-Δ/T) over the range of 0.6-300 K with Δ = 123.6 K. The magnetization of the film becomes saturated in a relatively low field with a small coercive field. The temperature dependence of magnetization shows Bloch's T3/2 law and the slope of the curve suggests a critical wavelength of λΔ 26.6 Å beyond which spin-flip scattering becomes important.

  2. Real-time Measurement of Secondary Organic Aerosols From The Photo-oxidation of Toluene Using Atmospheric Pressure Chemical Ionisation Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Collin, F.; Arias, M. C.; Merritt, J. V.; Hastie, D. R.

    A system has been developed to study the chemical composition of secondary or- ganic aerosol (SOA) from the photo-oxidation of hydrocarbons using real-time atmo- spheric pressure chemical ionisation triple quadrupole mass spectrometry (APCI/MS- MS) analysis. To complement existing work with a smog chamber, a two-litre dynamic reaction cell has been built. This has a residence time of around two minutes (instead of several hours for smog chamber experiments), thus permitting on-line analysis. Sample gases are introduced into the air stream and irradiated by a 1000 W xenon arc lamp. Af- ter dilution, some of the mixture from the reaction cell is introduced in the MS ion source via a heated probe, with the particle number density being determined by a condensation nucleus counter on the remainder. The focus so far has been on SOA from the photo-oxidation of toluene by HO radicals in presence of NO, with the HO radicals being generated by the photolysis of Isopy- lNitrite (IPN). Prior to performing analyses on the SOA, target compounds (detected in the particulate phase in other studies) were selected and three ions designated to make a fingerprint for each compound. Finally, by using either a denuder, a granu- lar bed diffusion battery or a filter, both gas and particulate phases have been studied independently and compared. Preliminary results show that a number of target compounds, such as methylglyoxylic acid, benzaldehyde or cresol, have been detected in both gas and particulate phases. Most of these compounds appear to be present mainly in the gas phase. An exhaustive identification of organic compounds is a part of the on-going work.

  3. An Atmospheric Pressure Ping-Pong "Ballometer"

    ERIC Educational Resources Information Center

    Kazachkov, Alexander; Kryuchkov, Dmitriy; Willis, Courtney; Moore, John C.

    2006-01-01

    Classroom experiments on atmospheric pressure focus largely on demonstrating its existence, often in a most impressive way. A series of amusing physics demonstrations is widely known and practiced by educators teaching the topic. However, measuring the value of atmospheric pressure(P[subscript atm]) is generally done in a rather mundane way,…

  4. Ultrapressure liquid chromatography-tandem mass spectrometry assay using atmospheric pressure photoionization (UPLC-APPI-MS/MS) for quantification of 4-methoxydiphenylmethane in pharmacokinetic evaluation.

    PubMed

    Farhan, Nashid; Fitzpatrick, Sean; Shim, Yun M; Paige, Mikell; Chow, Diana Shu-Lian

    2016-09-01

    4-Methoxydiphenylmethane (4-MDM), a selective augmenter of Leukotriene A4 Hydrolase (LTA4H), is a new anti-inflammatory compound for potential treatment of chronic obstructive pulmonary disease (COPD). Currently, there is no liquid chromatography tandem mass spectrometric (LC-MS/MS) method for the quantification of 4-MDM. A major barrier for developing the LC-MS/MS method is the inability of electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) to ionize 4-MDM due to its hydrophobicity and lack of any functional group for ionization. With the advent of atmospheric pressure photoionization (APPI) technique, many hydrophobic compounds have been demonstrated to ionize by charge transfer reactions. In this study, a highly sensitive ultrapressure liquid chromatography tandem mass spectrometry assay using atmospheric pressure photoionization (UPLC-APPI-MS/MS) for the quantifications of 4-MDM in rat plasma has been developed and validated. 4-MDM was extracted from the plasma by solid phase extraction (SPE) and separated chromatographically using a reverse phase C8 column. The photoionization (PI) was achieved by introducing anisole as a dopant to promote the reaction of charge transfer. The assay with a linear range of 5 (LLOQ)-400ngmL(-1) met the regulatory requirements for accuracy, precision and stability. The validated assay was employed to quantify the plasma concentrations of 4-MDM after an oral dosing in Sprague Dawley (SD) rats. PMID:27232150

  5. Liquid chromatography/mass spectrometric determination of patulin in apple juice using atmospheric pressure photoionization.

    PubMed

    Takino, Masahiko; Daishima, Shigeki; Nakahara, Taketoshi

    2003-01-01

    This paper describes a comparison between atmospheric pressure chemical ionization (APCI) and the recently introduced atmospheric pressure photoionization (APPI) technique for the liquid chromatography/mass spectrometric (LC/MS) determination of patulin in clear apple juice. A column switching technique for on-line extraction of clear apple juice was developed. The parameters investigated for the optimization of APPI were the ion source parameters fragmentor voltage, capillary voltage, and vaporizer temperature, and also mobile phase composition and flow rate. Furthermore, chemical noise and signal suppression of analyte signals due to sample matrix interference were investigated for both APCI and APPI. The results indicated that APPI provides lower chemical noise and signal suppression in comparison with APCI. The linear range for patulin in apple juice (correlation coefficient >0.999) was 0.2-100 ng mL(-1). Mean recoveries of patulin in three apple juices ranged from 94.5 to 103.2%, and the limit of detection (S/N = 3), repeatability and reproducibility were 1.03-1.50 ng mL(-1), 3.9-5.1% and 7.3-8.2%, respectively. The total analysis time was 10.0 min. PMID:12913860

  6. Microwave-assisted atmospheric pressure plasma polymerization of hexamethyldisiloxane

    NASA Astrophysics Data System (ADS)

    Matsubayashi, Toshiki; Hidaka, Hiroki; Muguruma, Hitoshi

    2016-07-01

    Microwave-assisted atmospheric pressure plasma polymerization is presented. A system with a re-entrant microwave cavity realizes simple matching, stable plasma, and free space under the orifice of plasma steam. Hexamethyldisiloxane is employed as a monomer, while argon is used as a carrier gas. The effective area of the hydrophobic coating film used corresponds to a circle of 20 mm diameter and the deposition rate considered is 5 nm/min. Matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy shows that the coating film has a large molecular weight (>200 kDa), suggesting that a high-crosslinking and three-dimensional polymer matrix is formed and microwave-assisted atmospheric pressure plasma polymerization is fulfilled.

  7. Photochemistry of limonene secondary organic aerosol studied with chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, Xiang

    Limonene is one of the most abundant monoterpenes in the atmosphere. Limonene easily reacts with gas-phase oxidants in air such as NO3, ozone and OH. Secondary organic aerosol (SOA) is formed when low vapor pressure products condense into particles. Chemicals in SOA particles can undergo further reactions with oxidants and with solar radiation that significantly change SOA composition over the course of several days. The goal of this work was to characterize radiation induced reaction in SOA. To perform experiments, we have designed and constructed an Atmospheric Pressure Chemical Ionization Mass Spectrometer (APCIMS) coupled to a photochemical cell containing SOA samples. In APCIMS, (H2O)nH 3O+ clusters are generated in a 63Ni source and react with gaseous organic analytes. Most organic chemicals are not fragmented by the ionization process. We have focused our attention on limonene SOA prepared in two different ways. The first type of SOA is produced by oxidation of limonene by ozone; and the second type of SOA is formed by the NO3-induced oxidation of limonene. They model the SOA formed under daytime and nighttime conditions, respectively. Ozone initiated oxidation is the most important chemical sink for limonene both indoors, where it is used for cleaning purposes, and outdoors. Terpenes are primarily oxidized by reactions with NO3 at night time. We generated limonene SOA under different ozone and limonene concentrations. The resulting SOA samples were exposed to wavelength-tunable radiation in the UV-Visible range between 270 nm and 630 nm. The results show that the photodegradation rates strongly depend on radiation wavelengths. Gas phase photodegradation products such as acetone, formaldehyde, acetaldehyde, and acetic acid were shown to have different production rates for SOA formed in different concentration conditions. Even for SOA prepared under the lowest concentrations, the SOA photodegradation was efficient. The conclusion is that exposure of SOA to

  8. Low Temperature Atmospheric Pressure Plasma Sterilization Shower

    NASA Astrophysics Data System (ADS)

    Gandhiraman, R. P.; Beeler, D.; Meyyappan, M.; Khare, B. N.

    2012-10-01

    Low-temperature atmospheric pressure plasma sterilization shower to address both forward and backward biological contamination issues is presented. The molecular effects of plasma exposure required to sterilize microorganisms is also analysed.

  9. Soft x-ray spectroscopy in atmospheric pressure helium

    SciTech Connect

    Roper, M.D.; van der Laan, G.; Flaherty, J.V.; Padmore, H.A. )

    1992-01-01

    We report on an environmental chamber, which is attached to a UHV beamline, in which soft x-ray measurements can be done at atmospheric pressure in helium. X-ray measurements in air can only be performed at energies above about 3 keV because of the strong absorption of soft x rays by oxygen and nitrogen. However, a low-{ital Z} scatterer such as helium has a long absorption length for soft x rays even at atmospheric pressure. Thus, this new chamber allows soft x-ray experiments to be performed on samples with physical properties that are incompatible with UHV conditions, e.g., liquid and frozen aqueous solutions, corrosive materials, etc. A helium-tight tank has been installed behind the vacuum experimental chamber of the double crystal beamline 3.4 at the Daresbury SRS. The tank is purged with helium at atmospheric pressure and the gas in the tank is isolated from the high vacuum of the rest of the beamline by a thin mylar window which is supported on a capillary array. The tank contains a sample stage, two ionization chambers and a parallel-plate gas proportional counter for fluorescence detection of dilute samples, which has produced good results on the {ital K} edges of Cl, S, and P.

  10. Low-voltage back-gated atmospheric pressure chemical vapor deposition based graphene-striped channel transistor with high-κ dielectric showing room-temperature mobility > 11,000 cm(2)/V·s.

    PubMed

    Smith, Casey; Qaisi, Ramy; Liu, Zhihong; Yu, Qingkai; Hussain, Muhammad Mustafa

    2013-07-23

    Utilization of graphene may help realize innovative low-power replacements for III-V materials based high electron mobility transistors while extending operational frequencies closer to the THz regime for superior wireless communications, imaging, and other novel applications. Device architectures explored to date suffer a fundamental performance roadblock due to lack of compatible deposition techniques for nanometer-scale dielectrics required to efficiently modulate graphene transconductance (gm) while maintaining low gate capacitance-voltage product (CgsVgs). Here we show integration of a scaled (10 nm) high-κ gate dielectric aluminum oxide (Al2O3) with an atmospheric pressure chemical vapor deposition (APCVD)-derived graphene channel composed of multiple 0.25 μm stripes to repeatedly realize room-temperature mobility of 11,000 cm(2)/V·s or higher. This high performance is attributed to the APCVD graphene growth quality, excellent interfacial properties of the gate dielectric, conductivity enhancement in the graphene stripes due to low tox/Wgraphene ratio, and scaled high-κ dielectric gate modulation of carrier density allowing full actuation of the device with only ±1 V applied bias. The superior drive current and conductance at Vdd = 1 V compared to other top-gated devices requiring undesirable seed (such as aluminum and poly vinyl alcohol)-assisted dielectric deposition, bottom gate devices requiring excessive gate voltage for actuation, or monolithic (nonstriped) channels suggest that this facile transistor structure provides critical insight toward future device design and process integration to maximize CVD-based graphene transistor performance. PMID:23777434

  11. Tantalum Etching with an Atmospheric Pressure Plasma Jet

    NASA Astrophysics Data System (ADS)

    Teslow, Hilary; Herrmann, Hans; Rosocha, Louis

    2002-10-01

    The APPJ is a non-thermal, atmospheric-pressure, glow discharge. A feedgas, composed of an inert carrier gas (e.g., He) and small concentrations of additives (e.g., O2, or CF4), flows between closely spaced electrodes powered at 13.56 MHz rf in a coaxial or parallel plate arrangement. The plasma has Te ˜ 2 eV and ne ˜ 10^11 cm-3. Electrons are not in thermal equilibrium with ions and neutrals: the electrons are ``hot", while the overall gas temperature is quite ``cold", typically 50-300 C. In the plasma, the gas is excited, dissociated or ionized by energetic electron impact. As the gas exits the discharge volume, ions and electrons are rapidly lost by recombination, leaving metastables (e.g. O2*, He*) and radicals (e.g. O, F, OF, O2F, CFO). These reactive species are then directed onto a surface to be processed. The APPJ has been developed for decontaminating nuclear, chemical, and biological agents. Atomic fluorine, and possibly other reactive species, can be used to convert actinides (e.g., U and Pu), into volatile fluorides (e.g., UF6, PuF6) that can be trapped, resulting in significant volume reduction of radioactive waste. In this talk, we will present results on using Ta as a surrogate for Pu in He/O2/CF4 etching plasmas. Results of experimental measurements of Ta etch rates for various gas mixtures and plasma jet standoff distance will be compared with plasma chemistry modeling of the concentrations of several active species produced in the plasma.

  12. Ambient Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Huang, Min-Zong; Yuan, Cheng-Hui; Cheng, Sy-Chyi; Cho, Yi-Tzu; Shiea, Jentaie

    2010-07-01

    Mass spectrometric ionization methods that operate under ambient conditions and require minimal or no sample pretreatment have attracted much attention in such fields as biomedicine, food safety, antiterrorism, pharmaceuticals, and environmental pollution. These technologies usually involve separate ionization and sample-introduction events, allowing independent control over each set of conditions. Ionization is typically performed under ambient conditions through use of existing electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) techniques. Rapid analyses of gas, liquid, and solid samples are possible with the adoption of various sample-introduction methods. This review sorts different ambient ionization techniques into two main subcategories, primarily on the basis of the ionization processes, that are further differentiated in terms of the approach used for sampling.

  13. Selective Mass Spectrometer Characterization of Halogen Gases in Air at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Dahl, S.; Ivey, M. M.; Foster, K. L.

    2004-12-01

    We have developed a new interface for use with a commercial ion-trap mass spectrometer equipped with atmospheric pressure chemical ionization (APCI-MS). The new interface uses a mechanical pump to draw gaseous analyte through a glass manifold and into the corona discharge area of the APCI-MS. This new method of delivering a gaseous sample at atmospheric pressure directly to the MS has been used to obtain real-time measurements of Br2 and Cl2 over synthetic seawater ice. The ion intensity of a halogen gas measured by the MS is affected by the pumping rate and the position of the glass manifold. The MS signals for Br2 are linear in the 0.1 to 10.6 ppbv range, and the estimated 3 sigma detection limit is 20.7 pptv. The MS signals for Cl2 are linear in the 0.2 to 25 ppbv range, and the estimated 3 sigma detection limit is 1.081 ppbv. This lab-based technique is suitable to be the basis for a portable field-based design. Such a design, a miniaturized instrument, will help elucidate the role of seawater snow and ice surfaces on the photochemical production of Br2 and Cl2 in the high Arctic.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

  15. Effect of Swirling Desolvation Gas Flow in an Atmospheric Pressure Ion Source

    NASA Astrophysics Data System (ADS)

    Savtchenko, Serguei; Ashgriz, Nasser; Jolliffe, Chuck; Cousins, Lisa; Gamble, Heather

    2014-09-01

    A numerical study is performed to examine the effect of introducing a swirling desolvation gas flow on the flow transport characteristics in an electrospray and an atmospheric pressure chemical ionization (APCI) system. An ion source having three coaxial tubes is considered: (1) an inner capillary tube to inject the liquid sample, (2) a center coaxial tube to provide a room temperature gas flow to nebulize the liquid, referred to as the nebulizing gas flow, and (3) an outer coaxial tube having a converging exit to supply a high temperature gas for droplet desolvation, referred to as the desolvation gas flow. The results show that a swirling desolvation gas flow reduces the dispersion of the nebulizing gas and suppresses turbulent diffusion. The effect of swirling desolvation flow on the trajectory of a range of droplet sizes emitted from a source is also considered.

  16. Leidenfrost Phenomenon-assisted Thermal Desorption (LPTD) and Its Application to Open Ion Sources at Atmospheric Pressure Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

    2013-03-01

    This work describes the development and application of a new thermal desorption technique that makes use of the Leidenfrost phenomenon in open ion sources at atmospheric pressure for direct mass spectrometric detection of ultratrace levels of illicit, therapeutic, and stimulant drugs, toxicants, and peptides (molecular weight above 1 kDa) in their unaltered state from complex real world samples without or with minor sample pretreatment. A low temperature dielectric barrier discharge ion source was used throughout the experiments and the analytical figures of merit of this technique were investigated. Further, this desorption technique coupled with other ionization sources such as electrospray ionization (ESI) and dc corona discharge atmospheric pressure chemical ionization (APCI) in open atmosphere was also investigated. The use of the high-resolution `Exactive Orbitrap' mass spectrometer provided unambiguous identification of trace levels of the targeted compounds from complex mixtures and background noise; the limits of detection for various small organic molecules and peptides treated with this technique were at the level of parts per trillion and 10-9 M, respectively. The high sensitivity of the present technique is attributed to the spontaneous enrichment of analyte molecules during the slow evaporation of the solvent, as well as to the sequential desorption of molecules from complex mixtures based on their volatilities. This newly developed desorption technique is simple and fast, while molecular ions are observed as the major ions.

  17. Leidenfrost phenomenon-assisted thermal desorption (LPTD) and its application to open ion sources at atmospheric pressure mass spectrometry.

    PubMed

    Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

    2013-03-01

    This work describes the development and application of a new thermal desorption technique that makes use of the Leidenfrost phenomenon in open ion sources at atmospheric pressure for direct mass spectrometric detection of ultratrace levels of illicit, therapeutic, and stimulant drugs, toxicants, and peptides (molecular weight above 1 kDa) in their unaltered state from complex real world samples without or with minor sample pretreatment. A low temperature dielectric barrier discharge ion source was used throughout the experiments and the analytical figures of merit of this technique were investigated. Further, this desorption technique coupled with other ionization sources such as electrospray ionization (ESI) and dc corona discharge atmospheric pressure chemical ionization (APCI) in open atmosphere was also investigated. The use of the high-resolution 'Exactive Orbitrap' mass spectrometer provided unambiguous identification of trace levels of the targeted compounds from complex mixtures and background noise; the limits of detection for various small organic molecules and peptides treated with this technique were at the level of parts per trillion and 10(-9) M, respectively. The high sensitivity of the present technique is attributed to the spontaneous enrichment of analyte molecules during the slow evaporation of the solvent, as well as to the sequential desorption of molecules from complex mixtures based on their volatilities. This newly developed desorption technique is simple and fast, while molecular ions are observed as the major ions. PMID:23423791

  18. Does low atmospheric pressure independently trigger migraine?

    PubMed

    Bolay, Hayrunnisa; Rapoport, Alan

    2011-10-01

    Although atmospheric weather changes are often listed among the common migraine triggers, studies to determine the specific weather component(s) responsible have yielded inconsistent results. Atmospheric pressure change produces air movement, and low pressure in particular is associated with warm weather, winds, clouds, dust, and precipitation, but how this effect might generate migraine is not immediately obvious. Humans are exposed to low atmospheric pressure in situations such as ascent to high altitude or traveling by airplane in a pressurized cabin. In this brief overview, we consider those conditions and experimental data delineating other elements in the atmosphere potentially related to migraine (such as Saharan dust). We conclude that the available data suggest low atmospheric pressure unaccompanied by other factors does not trigger migraine. PMID:21906054

  19. Atmospheric Pressure Plasma Process And Applications

    SciTech Connect

    Peter C. Kong; Myrtle

    2006-09-01

    This paper provides a general discussion of atmospheric-pressure plasma generation, processes, and applications. There are two distinct categories of atmospheric-pressure plasmas: thermal and nonthermal. Thermal atmospheric-pressure plasmas include those produced in high intensity arcs, plasma torches, or in high intensity, high frequency discharges. Although nonthermal plasmas are at room temperatures, they are extremely effective in producing activated species, e.g., free radicals and excited state atoms. Thus, both thermal and nonthermal atmosphericpressure plasmas are finding applications in a wide variety of industrial processes, e.g. waste destruction, material recovery, extractive metallurgy, powder synthesis, and energy conversion. A brief discussion of recent plasma technology research and development activities at the Idaho National Laboratory is included.

  20. Surface Modification by Atmospheric Pressure Plasma for Improved Bonding

    NASA Astrophysics Data System (ADS)

    Williams, Thomas Scott

    An atmospheric pressure plasma source operating at temperatures below 150?C and fed with 1.0-3.0 volume% oxygen in helium was used to activate the surfaces of the native oxide on silicon, carbon-fiber reinforced epoxy composite, stainless steel type 410, and aluminum alloy 2024. Helium and oxygen were passed through the plasma source, whereby ionization occurred and ˜10 16 cm-3 oxygen atoms, ˜1015 cm -3 ozone molecules and ˜1016 cm-3 metastable oxygen molecules (O21Deltag) were generated. The plasma afterglow was directed onto the substrate material located 4 mm downstream. Surface properties of the plasma treated materials have been investigated using water contact angle (WCA), atomic force microscopy (AFM), infrared spectroscopy (IR), and x-ray photoelectron spectroscopy (XPS). The work presented herein establishes atmospheric-pressure plasma as a surface preparation technique that is well suited for surface activation and enhanced adhesive bond strength in a variety of materials. Atmospheric plasma activation presents an environmentally friendly alternative to wet chemical and abrasive methods of surface preparation. Attenuated total internal reflection infrared spectroscopy was used to study the aging mechanism of the native oxide on silicon. During storage at ambient conditions, the water contact angle of a clean surface increased from <5° to 40° over a period of 12 hours. When stored under a nitrogen purge, the water contact angle of a clean surface increased from <5° to 30° over a period of 40-60 hours. The change in contact angle resulted from the adsorption of nonanal onto the exposed surface hydroxyl groups. The rate of adsorption of nonanal under a nitrogen purged atmosphere ranged from 0.378+/-0.011 hr-1 to 0.182+/-0.008 hr -1 molecules/(cm2•s), decreasing as the fraction of hydrogen-bonded hydroxyl groups increased from 49% to 96% on the SiO 2 surface. The adsorption of the organic contaminant could be suppressed indefinitely by storing the

  1. Surface Modification by Atmospheric Pressure Plasma for Improved Bonding

    NASA Astrophysics Data System (ADS)

    Williams, Thomas Scott

    An atmospheric pressure plasma source operating at temperatures below 150?C and fed with 1.0-3.0 volume% oxygen in helium was used to activate the surfaces of the native oxide on silicon, carbon-fiber reinforced epoxy composite, stainless steel type 410, and aluminum alloy 2024. Helium and oxygen were passed through the plasma source, whereby ionization occurred and ˜10 16 cm-3 oxygen atoms, ˜1015 cm -3 ozone molecules and ˜1016 cm-3 metastable oxygen molecules (O21Deltag) were generated. The plasma afterglow was directed onto the substrate material located 4 mm downstream. Surface properties of the plasma treated materials have been investigated using water contact angle (WCA), atomic force microscopy (AFM), infrared spectroscopy (IR), and x-ray photoelectron spectroscopy (XPS). The work presented herein establishes atmospheric-pressure plasma as a surface preparation technique that is well suited for surface activation and enhanced adhesive bond strength in a variety of materials. Atmospheric plasma activation presents an environmentally friendly alternative to wet chemical and abrasive methods of surface preparation. Attenuated total internal reflection infrared spectroscopy was used to study the aging mechanism of the native oxide on silicon. During storage at ambient conditions, the water contact angle of a clean surface increased from <5° to 40° over a period of 12 hours. When stored under a nitrogen purge, the water contact angle of a clean surface increased from <5° to 30° over a period of 40-60 hours. The change in contact angle resulted from the adsorption of nonanal onto the exposed surface hydroxyl groups. The rate of adsorption of nonanal under a nitrogen purged atmosphere ranged from 0.378+/-0.011 hr-1 to 0.182+/-0.008 hr -1 molecules/(cm2•s), decreasing as the fraction of hydrogen-bonded hydroxyl groups increased from 49% to 96% on the SiO 2 surface. The adsorption of the organic contaminant could be suppressed indefinitely by storing the

  2. Simulation of low temperature atmospheric pressure corona discharge in helium

    NASA Astrophysics Data System (ADS)

    Bekasov, Vladimir; Kirsanov, Gennady; Eliseev, Stepan; Kudryavtsev, Anatoly; Sisoev, Sergey

    2015-11-01

    The main objective of this work was to construct a numerical model of corona discharge in helium at atmospheric pressure. The calculation was based on the two-dimensional hybrid model. Two different plasma-chemical models were considered. Models were built for RF corona and negative DC corona discharge. The system of equations is solved by the finite element method in the COMSOL Multiphysics. Main parameters of the discharge (the density of charged and excited particles, the electron temperature) and their dependence on the input parameters of the model (geometry, electrode voltage, power) were calculated. The calculations showed that the shape of the electron distribution near the electrode depends on the discharge power. The neutral gas heating data obtained will allow predicting the temperature of the gases at the designing of atmospheric pressure helium plasma sources.

  3. Simulation of low temperature atmospheric pressure corona discharge in helium

    NASA Astrophysics Data System (ADS)

    Bekasov, V.; Chirtsov, Alex; Demidova, Maria; Kudryavtsev, Anatoly

    2015-11-01

    The main objective of this work was to construct a numerical model of corona discharge in helium at atmospheric pressure. Calculations were based on the two-dimensional hybrid model. Two different plasma-chemical models were considered. Models were built for RF corona and negative DC corona discharges. The system of equations was solved by the finite element method in the COMSOL Multiphysics. Main parameters of the discharge (the density of charged and excited particles and the electron temperature) and their dependence on the input parameters of the model (geometry, electrode voltage and power) were calculated. The calculations showed that the shape of the electron distribution near the electrode depends on the discharge power. The neutral gas heating data obtained will allow for the prediction of the temperature of the gases in atmospheric pressure helium plasma sources. This work was supported by Russian Science Foundation (project 14-19-00311).

  4. Generation Of Atmospheric Pressure Non-Thermal Plasma By Diffusive And Constricted Discharges In Rest And Flowing Gases (Air And Nitrogen)

    NASA Astrophysics Data System (ADS)

    Akishev, Y.; Grushin, M.; Karalnik, V.; Kochetov, I.; Napartovich A.; Trushkin N.

    2010-07-01

    Weekly ionized non-thermal plasma (NTP) is of great interest for many applications because of its strong non-equilibrium state wherein an average electron energy Te exceeds markedly gas temperature Tg, i.e. electrons in the NTP are strongly overheated compared to neutral gas. Energetic electrons due to frequent collisions with the neutrals excite and dissociate effectively atoms and molecules of the plasma-forming gas that results in a creation of physically-, and bio-chemically active gaseous medium in a practically cold background gas. At present there are many kinds of plasma sources working at low and atmospheric pressure and using MW, RF, low frequency, pulsed and DC power supplies for NTP generation. The NTP at atmospheric pressure is of considerable interest for practice. A reason is that sustaining the NTP at atmospheric pressure at first allows us to avoid the use of expensive vacuum equipment and second gives opportunity to use the NTP for treatment of the exhausted gases and polluted liquids. The second opportunity cannot be realized at all with use of the NTP at low pressure. Main subject of this talk is low current atmospheric pressure gas discharges powering with DC power supplies. Plasma forming gases are air and nitrogen which are much cheaper compared to rare gases like He or Ar. Besides, great interest to molecular nitrogen as plasma forming gas is caused first of all its unique capability to accumulate huge energy in vibration, electron (metastables) and dissociated (atomic) states providing high chemical reactivity of the activated nitrogen. All active particles mentioned above have a long lifetime, and they can be therefore transported for a long distance away from place of their generation. Different current modes (diffusive and constricted) of these discharges are discussed. Experimental and numerical results on generation of chemically active species in the diffusive and constricted mode are presented. Some data on the usage of the

  5. Atmospheric-pressure plasma synthesis of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Nozaki, Tomohiro; Yoshida, Shinpei; Karatsu, Takuya; Okazaki, Ken

    2011-05-01

    An atmospheric-pressure radio-frequency discharge (APRFD) has great advantages over vacuum-oriented plasma-enhanced chemical vapour deposition (PECVD) as well as other types of atmospheric-pressure plasma sources in terms of single-walled carbon nanotube (SWCNT) growth. We first provide an overview on the recent advances in PECVD synthesis of CNTs, ranging from low pressure to atmospheric pressure, and then we present our current work focusing on the analysis of reactive species generated in the cathodic plasma sheath for further understanding of the SWCNT growth mechanism in PECVD. It was found that the plasma-generated C2H2 is the main CNT growth precursor in PECVD. Approximately 30% of the CH4 (initial feedstock) was converted into C2H6, C2H4 and C2H2. A trace amount of C2H2 enabled the synthesis of SWCNTs in the thermal chemical vapour deposition (CVD) regime. H2 is necessary to grow SWCNTs using PECVD because H2 suppresses the formation of excess amount of C2H2; however, H2 does not eliminate amorphous carbon even at H2/C2H2 ratios of 300. PECVD using a binary mixture of C2H2 and isotope-modified 13CH4 demonstrated that CH4 does not contribute to CNT growth in C2H2-assisted thermal CVD. Atmospheric-pressure PECVD performed with a He/CH4/H2 system is equivalent to C2H2-assisted thermal CVD without an etching gas. APRFD appears to produce a hidden species, which influences the CNT growth process.

  6. Application of atmospheric pressure plasma in polymer and composite adhesion

    NASA Astrophysics Data System (ADS)

    Yu, Hang

    An atmospheric pressure helium and oxygen plasma was used to investigate surface activation and bonding in polymer composites. This device was operated by passing 1.0-3.0 vol% of oxygen in helium through a pair of parallel plate metal electrodes powered by 13.56 or 27.12 MHz radio frequency power. The gases were partially ionized between the capacitors where plasma was generated. The reactive species in the plasma were carried downstream by the gas flow to treat the substrate surface. The temperature of the plasm gas reaching the surface of the substrate did not exceed 150 °C, which makes it suitable for polymer processing. The reactive species in the plasma downstream includes ~ 1016-1017 cm-3 atomic oxygen, ~ 1015 cm-3 ozone molecule, and ~ 10 16 cm-3 metastable oxygen molecule (O2 1Deltag). The substrates were treated at 2-5 mm distance from the exit of the plasma. Surface properties of the substrates were characterized using water contact angle (WCA), atomic force microscopy (AFM), infrared spectroscopy (IR), and X-ray photoelectron spectroscopy (XPS). Subsequently, the plasma treated samples were bonded adhesively or fabricated into composites. The increase in mechanical strength was correlated to changes in the material composition and structure after plasma treatment. The work presented hereafter establishes atmospheric pressure plasma as an effective method to activate and to clean the surfaces of polymers and composites for bonding. This application can be further expanded to the activation of carbon fibers for better fiber-resin interactions during the fabrication of composites. Treating electronic grade FR-4 and polyimide with the He/O2 plasma for a few seconds changed the substrate surface from hydrophobic to hydrophilic, which allowed complete wetting of the surface by epoxy in underfill applications. Characterization of the surface by X-ray photoelectron spectroscopy shows formation of oxygenated functional groups, including hydroxyl, carbonyl, and

  7. Dielectric barrier discharge ionization for liquid chromatography/mass spectrometry.

    PubMed

    Hayen, Heiko; Michels, Antje; Franzke, Joachim

    2009-12-15

    An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry (LC/MS). For this purpose, the plasma was realized in a commercial atmospheric pressure ionization source. Dielectric barrier discharge ionization (DBDI) was compared to conventional electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) in the positive ionization mode. Therefore, a heterogeneous compound library was investigated that covered polar compounds such as amino acids, water-soluble vitamins, and nonpolar compounds like polycyclic aromatic hydrocarbons and functionalized hydrocarbons. It turned out that DBDI can be regarded as a soft ionization technique characterized by only minor fragmentation similar to APCI. Mainly protonated molecules were detected. Additionally, molecular ions were observed for polycyclic aromatic hydrocarbons and derivatives thereof. During DBDI, adduct formation with acetonitrile occurred. For aromatic compounds, addition of one to four oxygen atoms and to a smaller extend one nitrogen and oxygen was observed which delivered insight into the complexity of the ionization processes. In general, compounds covering a wider range of polarities can be ionized by DBDI than by ESI. Furthermore, limits of detection compared to APCI are in most cases equal or even better. PMID:19911793

  8. Runaway electron beam in atmospheric pressure discharges

    NASA Astrophysics Data System (ADS)

    Oreshkin, E. V.; Barengolts, S. A.; Chaikovsky, S. A.; Oreshkin, V. I.

    2015-11-01

    A numerical simulation was performed to study the formation of a runaway electron (RAE) beam from an individual emission zone in atmospheric pressure air discharges with a highly overvolted interelectrode gap. It is shown that the formation of a RAE beam in discharges at high overvoltages is much contributed by avalanche processes.

  9. Determining Atmospheric Pressure Using a Water Barometer

    ERIC Educational Resources Information Center

    Lohrengel, C. Frederick, II; Larson, Paul R.

    2012-01-01

    The atmosphere is an envelope of compressible gases that surrounds Earth. Because of its compressibility and nonuniform heating by the Sun, it is in constant motion. The atmosphere exerts pressure on Earth's surface, but that pressure is in constant flux. This experiment allows students to directly measure atmospheric pressure by measuring the…

  10. Simultaneous determination of creatinine, creatine, and guanidinoacetic acid in human serum and urine using liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Yasuda, M; Sugahara, K; Zhang, J; Ageta, T; Nakayama, K; Shuin, T; Kodama, H

    1997-11-15

    A rapid and direct method for simultaneous determination of creatinine, creatine, and guanidinoacetic acid in biological samples has been developed by using column liquid chromatography-mass spectrometry (LC/APCI-MS). The determinations of creatinine, creatine, and guanidinoacetic acid in the samples of human urine and serum were carried out by scanning the [M + H]+ ions of each compound. The recoveries of authentic compounds were 93.87 +/- 6.00% (n = 5) for creatinine, 94.80 +/- 8.93% (n = 5) for creatine, and 90. 92 +/- 7.96% (n = 5) for guanidinoacetic acid after ion-exchange resin treatment. The content of creatinine in human urine and serum was also measured by the Jaffé method, a common method of determination of creatinine currently used in hospitals. The contents of creatinine, creatine, and guanidinoacetic acid obtained using LC/APCI-MS coincided well with those reported in previous papers. PMID:9367508

  11. Possible degradation/biotransformation of lutein in vitro and in vivo: isolation and structural elucidation of lutein metabolites by HPLC and LC-MS (atmospheric pressure chemical ionization).

    PubMed

    Lakshminarayana, Rangaswamy; Aruna, Gorusupudi; Sangeetha, Ravi Kumar; Bhaskar, Narayan; Divakar, Sounder; Baskaran, Vallikannan

    2008-10-01

    Metabolites of lutein are highly concentrated in the human macula and are known to provide protection against age-related macular degeneration. The aim of this investigation was to characterize the in vitro oxidation products of lutein obtained through photo-oxidation and to compare them with biologically transformed dietary lutein in intestine, plasma, liver, and eyes of rats. In vivo studies involved feeding rats a diet devoid of lutein for 2 weeks to induce deficiency. Rats were divided into two equal groups (n=6/group) and received either micellar lutein by gavage for 10 days or diet supplemented with fenugreek leaves as a lutein source for 4 weeks. Lutein metabolites/oxidation products obtained from in vivo and in vitro studies were characterized by HPLC and LC-MS (APCI) techniques to elucidate their structure. The characteristic fragmented ions resulting from photo-oxidation of lutein were identified as 523 (M(+)+H(+)-3CH(3)), 476 (M(+)+H(+)-6CH(3)), and 551 (M(+)+H(+)-H(2)O). In the eyes, the fragmented molecules resulting from lutein were 13-Z lutein, 13'-Z lutein, 13-Z zeaxanthin, all-E zeaxanthin, 9-Z lutein, 9'-Z lutein, and 3'-oxolutein. Epoxycarotenoids were identified in liver and plasma, whereas anhydrolutein was identified in intestine. This study emphasizes the essentiality of dietary lutein to maintain its status in the retina. PMID:18640265

  12. Two-step cleanup procedure for the identification of carotenoid esters by liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Rodrigues, Daniele Bobrowski; Mariutti, Lilian Regina Barros; Mercadante, Adriana Zerlotti

    2016-07-29

    Carotenoids are naturally found in both free form and esterified with fatty acids in most fruits; however, up to now the great majority of studies only evaluated their composition after saponification. This fact is easily explained by the difficult to analyze carotenoid esters. Preliminary studies showed that cleanup procedures in the extract are necessary for further analysis by LC-MS/MS since triacylglycerols (TAGs) impair the MS detection. Considering these facts, we developed a new cleanup procedure to remove TAGs and other lipids from carotenoid fruit extracts. This procedure is based on physical removal of solid lipids at low temperature followed by open column chromatography on MgO and diatomaceous earth. Before cleanup, four carotenoid diesters and two free xanthophylls were identified in murici (Byrsonyma crassifolia), corresponding to about 65% of the total chromatogram area. After carrying out the two-step cleanup procedure, 35 carotenoids were identified, being 14 monoesters, six free carotenoids and 15 carotenoid diesters. We can conclude that this two-step procedure was successfully applied to murici, an Amazonian fruit, which contains high amounts of lipids. PMID:27371019

  13. Characterizations of atmospheric pressure low temperature plasma jets and their applications

    NASA Astrophysics Data System (ADS)

    Karakas, Erdinc

    2011-12-01

    Atmospheric pressure low temperature plasma jets (APLTPJs) driven by short pulses have recently received great attention because of their potential in biomedical and environmental applications. This potential is due to their user-friendly features, such as low temperature, low risk of arcing, operation at atmospheric pressure, easy handheld operation, and low concentration of ozone generation. Recent experimental observations indicate that an ionization wave exists and propagates along the plasma jet. The plasma jet created by this ionization wave is not a continuous medium but rather consists of a bullet-like-structure known as "Plasma Bullet". More interestingly, these plasma bullets actually have a donut-shaped makeup. The nature of the plasma bullet is especially interesting because it propagates in the ambient air at supersonic velocities without any externally applied electric field. In this dissertation, experimental insights are reported regarding the physical and chemical characteristics of the APLTPJs. The dynamics of the plasma bullet are investigated by means of a high-speed ICCD camera. A plasma bullet propagation model based on the streamer theory is confirmed with adequate explanations. It is also found that a secondary discharge, ignited by the charge accumulation on the dielectric electrode surfaces at the end of the applied voltage, interrupts the plasma bullet propagation due to an opposing current along the ionization channel. The reason for this interesting phenomenon is explained in detail. The plasma bullet comes to an end when the helium mole fraction along the ionization channel, or applied voltage, or both, are less than some critical values. The presence of an inert gas channel in the surrounding air, such as helium or argon, has a critical role in plasma bullet formation and propagation. For this reason, a fluid dynamics study is employed by a commercially available simulation software, COMSOL, based on finite element method. Spatio

  14. UPTAKE OF IONIZABLE ORGANIC CHEMICALS AT FISH GILLS

    EPA Science Inventory

    Uptake of organic acids by fish, and their toxicity, generally decrease with increasing pH above the pK, presumably due to neutral forms of such chemicals being more readily adsorbed than their ionized forms. However, uptake usually exceeds that expected based just on the concent...

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

    PubMed Central

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

    2016-01-01

    Abstract Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI‐APi‐TOF (Chemical Ionization‐Atmospheric Pressure interface‐Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI‐APi‐TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4‐H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self‐contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit. PMID:27610289

  16. Competitive Deprotonation and Superoxide [O₂⁻•)] Radical-Anion Adduct Formation Reactions of Carboxamides under Negative-Ion Atmospheric-Pressure Helium-Plasma Ionization (HePI) Conditions.

    PubMed

    Hassan, Isra; Pinto, Spencer; Weisbecker, Carl; Attygalle, Athula B

    2016-03-01

    Carboxamides bearing an N-H functionality are known to undergo deprotonation under negative-ion-generating mass spectrometric conditions. Herein, we report that N-H bearing carboxamides with acidities lower than that of the hydroperoxyl radical (HO-O(•)) preferentially form superoxide radical-anion (O2(-•)) adducts, rather than deprotonate, when they are exposed to the glow discharge of a helium-plasma ionization source. For example, the spectra of N-alkylacetamides show peaks for superoxide radical-anion (O2(-•)) adducts. Conversely, more acidic amides, such as N-alkyltrifluoroacetamides, preferentially undergo deprotonation under similar experimental conditions. Upon collisional activation, the O2(-•) adducts of N-alkylacetamides either lose the neutral amide or the hydroperoxyl radical (HO-O(•)) to generate the superoxide radical-anion (m/z 32) or the deprotonated amide [m/z (M - H)(-)], respectively. For somewhat acidic carboxamides, the association between the two entities is weak. Thus, upon mildest collisional activation, the adduct dissociates to eject the superoxide anion. Superoxide-adduct formation results are useful for structure determination purposes because carboxamides devoid of a N-H functionality undergo neither deprotonation nor adduct formation under HePI conditions. PMID:26545766

  17. Competitive Deprotonation and Superoxide [O2 -•] Radical-Anion Adduct Formation Reactions of Carboxamides under Negative-Ion Atmospheric-Pressure Helium-Plasma Ionization (HePI) Conditions

    NASA Astrophysics Data System (ADS)

    Hassan, Isra; Pinto, Spencer; Weisbecker, Carl; Attygalle, Athula B.

    2016-03-01

    Carboxamides bearing an N-H functionality are known to undergo deprotonation under negative-ion-generating mass spectrometric conditions. Herein, we report that N-H bearing carboxamides with acidities lower than that of the hydroperoxyl radical (HO-O•) preferentially form superoxide radical-anion (O2 -•) adducts, rather than deprotonate, when they are exposed to the glow discharge of a helium-plasma ionization source. For example, the spectra of N-alkylacetamides show peaks for superoxide radical-anion (O2 -•) adducts. Conversely, more acidic amides, such as N-alkyltrifluoroacetamides, preferentially undergo deprotonation under similar experimental conditions. Upon collisional activation, the O2 -• adducts of N-alkylacetamides either lose the neutral amide or the hydroperoxyl radical (HO-O•) to generate the superoxide radical-anion ( m/z 32) or the deprotonated amide [ m/z (M - H)-], respectively. For somewhat acidic carboxamides, the association between the two entities is weak. Thus, upon mildest collisional activation, the adduct dissociates to eject the superoxide anion. Superoxide-adduct formation results are useful for structure determination purposes because carboxamides devoid of a N-H functionality undergo neither deprotonation nor adduct formation under HePI conditions.

  18. Modeling atmospheric pressure plasmas for biomedical applications

    NASA Astrophysics Data System (ADS)

    Graves, David

    2007-10-01

    The use of cold, atmospheric pressure plasmas for biomedical treatments is an exciting new application in gaseous electronics. Investigations to date include various tissue treatments and surgery, bacterial destruction, and the promotion of wound healing, among others. In this talk, I will present results from modeling the `plasma needle,' an atmospheric pressure plasma configuration that has been explored by several groups around the world. The biomedical efficacy of the plasma needle has been demonstrated but the mechanisms of cell and tissue modification or bacterial destruction are only just being established. One motivation for developing models is to help interpret experiments and evaluate postulated mechanisms. The model reveals important elements of the plasma needle sustaining mechanisms and operating modes. However, the extraordinary complexity of plasma-tissue interactions represents a long-term challenge for this burgeoning field.

  19. Research on atmospheric pressure plasma processing sewage

    NASA Astrophysics Data System (ADS)

    Song, Gui-cai; Na, Yan-xiang; Dong, Xiao-long; Sun, Xiao-liang

    2013-08-01

    The water pollution has become more and more serious with the industrial progress and social development, so it become a worldwide leading environmental management problem to human survival and personal health, therefore, countries are looking for the best solution. Generally speaking, in this paper the work has the following main achievements and innovation: (1) Developed a new plasma device--Plasma Water Bed. (2) At atmospheric pressure condition, use oxygen, nitrogen, argon and helium as work gas respectively, use fiber spectrometer to atmospheric pressure plasma discharge the emission spectrum of measurement, due to the different work gas producing active particle is different, so can understand discharge, different particle activity, in the treatment of wastewater, has the different degradation effects. (3) Methyl violet solution treatment by plasma water bed. Using plasma drafting make active particles and waste leachate role, observe the decolorization, measurement of ammonia nitrogen removal.

  20. Graphene Membranes for Atmospheric Pressure Photoelectron Spectroscopy.

    PubMed

    Weatherup, Robert S; Eren, Baran; Hao, Yibo; Bluhm, Hendrik; Salmeron, Miquel B

    2016-05-01

    Atmospheric pressure X-ray photoelectron spectroscopy (XPS) is demonstrated using single-layer graphene membranes as photoelectron-transparent barriers that sustain pressure differences in excess of 6 orders of magnitude. The graphene serves as a support for catalyst nanoparticles under atmospheric pressure reaction conditions (up to 1.5 bar), where XPS allows the oxidation state of Cu nanoparticles and gas phase species to be simultaneously probed. We thereby observe that the Cu(2+) oxidation state is stable in O2 (1 bar) but is spontaneously reduced under vacuum. We further demonstrate the detection of various gas-phase species (Ar, CO, CO2, N2, O2) in the pressure range 10-1500 mbar including species with low photoionization cross sections (He, H2). Pressure-dependent changes in the apparent binding energies of gas-phase species are observed, attributable to changes in work function of the metal-coated grids supporting the graphene. We expect atmospheric pressure XPS based on this graphene membrane approach to be a valuable tool for studying nanoparticle catalysis. PMID:27082434

  1. Nanoparticle heating in atmospheric pressure plasmas

    NASA Astrophysics Data System (ADS)

    Kramer, Nicolaas; Aydil, Eray; Kortshagen, Uwe

    2015-09-01

    The plasma environment offers a number of attractive properties that allow for the generation of nanoparticle materials that are otherwise hard to produce by other means. Among these are the generally high temperatures that nanoparticles can attain within plasmas, enabling the generation of nanocrystals of high melting point materials. In low pressure discharges, these high temperatures are the result of energetic surface reactions that strongly heat the small nanoparticles combined with the relatively slow heat transfer to the neutral gas. At atmospheric pressure, the nanoparticle intrinsic temperature is much more closely coupled to the neutral gas temperature. We study the heating of nanoparticles in atmospheric pressure plasmas based on a Monte Carlo simulation that takes into account the most important plasma-surface reactions as well as the conductive cooling of nanoparticles through the neutral gas. We find that, compared to low pressure plasmas, significantly higher plasma densities and densities of reactive species are required in order to achieve nanoparticle temperatures comparable to those in low pressure plasmas. These findings have important implications for the application of atmospheric pressure plasmas for the synthesis of nanoparticle materials. This work was supported by the DOE Plasma Science Center for Predictive Control of Plasma Kinetics.

  2. Carbon nanofibers synthesized by decomposition of alcohol at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Jiang, N.; Koie, R.; Inaoka, T.; Shintani, Y.; Nishimura, K.; Hiraki, A.

    2002-07-01

    In the present study, we fabricated the carbon nanofibers (CNFs) by decomposition of methyl alcohol at atmospheric pressure. The CNFs were grown on Ni/Si substrates using simplified hot-filament chemical vapor deposition equipment. The deposits mainly consist of the semicrystalline CNFs, in which a few of carbon nanotubes are included. On the 30-nm-thick Ni/Si substrates, the mean length of the CNFs is 2-3 mum, and their average diameter is less than 100 nm. The as-deposited CNFs were evaluated by both scanning and transmission electron microscopes. The field-electron-emission properties of CNFs were characterized as well.

  3. Plasma printing: patterned surface functionalisation and coating at atmospheric pressure.

    PubMed

    Penache, C; Gessner, C; Betker, T; Bartels, V; Hollaender, A; Klages, C-P

    2004-08-01

    A new plasma-based micropatterning technique, here referred to as plasma printing, combines the well known advantages given by the nonequilibrium character of a dielectric barrier discharge (DBD) and its operation inside small gas volumes with dimension between tens and hundreds of micrometres. The discharge is run at atmospheric pressure and can be easily implemented for patterned surface treatment with applications in biotechnology and microtechnology. In this work the local modification of dielectric substrates, e.g. polymeric films, is addressed with respect to coating and chemical functionalisation, immobilisation of biomolecules and area-selective electroless plating. PMID:16475858

  4. Multiple (eight) plasma bullets in helium atmospheric pressure plasma jet and the role of nitrogen

    NASA Astrophysics Data System (ADS)

    Park, Sanghoo; Youn Moon, Se; Choe, Wonho

    2013-11-01

    As many as eight multiple plasma bullets produced at atmospheric pressure were observed in one voltage period in a capillary helium dielectric barrier plasma jet. We found that the number of the bullets strongly depends on the nitrogen fraction added to the helium supply gas. Using optical emission spectroscopy and ionization rate calculation, this study demonstrates that nitrogen gas plays an important role in the generation and dynamics of multiple plasma bullets through Penning ionization of nitrogen by helium metastables.

  5. Gasification and Ionization of Chemically Complex Liquids for FRC Injection

    NASA Astrophysics Data System (ADS)

    Holmes, Michael; Hill, Carrie

    2014-10-01

    Ion thrusters provide reliable and efficient spacecraft propulsion but are limited to noble gas propellants to limit chemical attack of components. However, thrusters based on Field Reversed Configuration (FRC) plasmas are becoming a reality. High beta compact-toroids are generated within an FRC thruster and then expelled to provide thrust. The closed field lines restrict the plasma from attacking thruster components. More convenient propellants such as water are therefore possible. The FRC thruster would generate a series of compact-toroids (plasmoids) to develop continuous spacecraft thrust. Each plasmoid ejection would empty the discharge region. The feed system would then refill the discharge region with partially ionized gas for the next discharge. The ionization part of this feed system is the subject of this paper. The question is how to produce a uniform, chemically complex, ionized gas within the discharge region that optimizes compact-toroid formation? We will be measuring chemical state, ionization state, and uniformity as the propellant enters the discharge region.

  6. Electron heating in radio-frequency capacitively coupled atmospheric-pressure plasmas

    SciTech Connect

    Liu, D. W.; Iza, F.; Kong, M. G.

    2008-12-29

    In atmospheric-pressure plasmas the main electron heating mechanism is Ohmic heating, which has distinct spatial and temporal evolutions in the {alpha} and {gamma} modes. In {gamma} discharges, ionizing avalanches in the sheaths are initiated not only by secondary electrons but also by metastable pooling reactions. In {alpha} discharges, heating takes place at the sheath edges and in contrast with low-pressure plasmas, close to 50% of the power absorbed by the electrons is absorbed at the edge of the retreating sheaths. This heating is due to a field enhancement caused by the large collisionality in atmospheric-pressure discharges.

  7. Spectroscopic diagnosis of an atmospheric-pressure waveguide-based microwave N2-Ar plasma torch

    NASA Astrophysics Data System (ADS)

    Li, Shou-Zhe; Chen, Chuan-Jie; Zhang, Xin; Zhang, Jialiang; Wang, Yong-Xing

    2015-04-01

    An atmospheric-pressure N2-Ar plasma is investigated by means of optical emission spectroscopic diagnosis concerning the variation of its fundamental parameters, electron density and plasma temperature, and concentrations of ionized molecular nitrogen, atomic nitrogen, and excited argon with the tuning variables, such as the input power and the ratio of N2 in N2-Ar mixture gas, in the discharge region of the plasma torch. Moreover, qualitative discussions are delivered with respect to the mechanisms for nitrogen dissociation and influence of the Ar component on the N2 plasma discharge at atmospheric pressure.

  8. A dielectric barrier discharge in neon at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Ran, Junxia; Luo, Haiyun; Wang, Xinxin

    2011-08-01

    A dielectric barrier discharge in neon at atmospheric pressure is investigated with electrical measurement and fast photography. It is found that a stable diffuse discharge can be easily generated in a gap with a gap space of 0.5-6 mm and is identified with a glow discharge. The first breakdown voltage of the gap is considerably higher than that of the same gap working in a stable diffuse discharge mode, which indicates that Penning ionization of neon metastables from the previous discharge with inevitable gas impurities plays an important role in the decrease in the breakdown voltage. Discharge patterns are observed in a gap shorter than 1 mm. From the experiments with a wedge-like gap, it is found that the discharge patterns are formed in the area with a higher applied electric field, which suggests that a higher applied electric field may cause a transition from a diffuse glow to discharge patterns.

  9. Response of cyanobacteria to low atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Qin, Lifeng; Yu, Qingni; Ai, Weidang; Tang, Yongkang; Ren, Jin; Guo, Shuangsheng

    2014-10-01

    Maintaining a low pressure environment in a controlled ecological life support system would reduce the technological complexity and resupply cost in the course of the construction of a future manned lunar base. To estimate the effect of a hypobaric environment in a lunar base on biological components, such as higher plants, microbes, and algae, cyanobacteria was used as the model by determining their response of growth, morphology, and physiology when exposed to half of standard atmospheric pressure for 16 days (brought back to standard atmospheric pressure 30 minutes every two days for sampling). The results indicated that the decrease of atmospheric pressure from 100 kPa to 50 kPa reduced the growth rates of Microcystis aeruginosa, Merismopedia sp., Anabaena sp. PCC 7120, and Anabaena flos-aquae. The ratio of carotenoid to chlorophyll a content in the four tested strains increased under low pressure conditions compared to ambient conditions, resulting from the decrease of chlorophyll a and the increase of carotenoid in the cells. Moreover, low pressure induced the reduction of the phycocyanin content in Microcystis aeruginosa, Anabaena sp. PCC 7120, and Anabaena flos-aquae. The result from the ultrastructure observed using SEM indicated that low pressure promoted the production of more extracellular polymeric substances (EPSs) compared to ambient conditions. The results implied that the low pressure environment of 50 kPa in a future lunar base would induce different effects on biological components in a CELSS, which must be considered during the course of designing a future lunar base. The results will be a reference for exploring the response of other biological components, such as plants, microbes, and animals, living in the life support system of a lunar base.

  10. Determining Atmospheric Pressure Using a Water Barometer

    NASA Astrophysics Data System (ADS)

    Lohrengel, C. Frederick; Larson, Paul R.

    2012-12-01

    The atmosphere is an envelope of compressible gases that surrounds Earth. Because of its compressibility and nonuniform heating by the Sun, it is in constant motion. The atmosphere exerts pressure on Earth's surface, but that pressure is in constant flux. This experiment allows students to directly measure atmospheric pressure by measuring the mass of the water that is used as the fluid medium in the barometer. Simple calculations based upon the mass of water collected from the barometer yield the mass of the atmosphere per square unit of area at the site where the experiment is conducted.

  11. Atmospheric-pressure plasma decontamination/sterilization chamber

    DOEpatents

    Herrmann, Hans W.; Selwyn, Gary S.

    2001-01-01

    An atmospheric-pressure plasma decontamination/sterilization chamber is described. The apparatus is useful for decontaminating sensitive equipment and materials, such as electronics, optics and national treasures, which have been contaminated with chemical and/or biological warfare agents, such as anthrax, mustard blistering agent, VX nerve gas, and the like. There is currently no acceptable procedure for decontaminating such equipment. The apparatus may also be used for sterilization in the medical and food industries. Items to be decontaminated or sterilized are supported inside the chamber. Reactive gases containing atomic and metastable oxygen species are generated by an atmospheric-pressure plasma discharge in a He/O.sub.2 mixture and directed into the region of these items resulting in chemical reaction between the reactive species and organic substances. This reaction typically kills and/or neutralizes the contamination without damaging most equipment and materials. The plasma gases are recirculated through a closed-loop system to minimize the loss of helium and the possibility of escape of aerosolized harmful substances.

  12. Self-consistent chemical model of partially ionized plasmas

    SciTech Connect

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

    2011-01-15

    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.

  13. Analytical vacuum force, atmospheric pressure dispute

    NASA Astrophysics Data System (ADS)

    Yongquan, Han

    Typically, the gap gas molecules is 10-9 m, since the center speed of the tornado is over 100 m / sec, it divided by the speed of a tornado, the gap of the gas molecules becomes 10-11m. Equivalent to the gap when there is no tornado that the gas molecules allow radiation to pass through, equivalent to the gap is reduced gas molecules 100 times by a tornado. There is no change in the Earth's radiate, the Earth's radiation is reduced to one percent of the original intensity by the radiation through the tornado periphery into the center of the tornado. According to the APS Division of Nuclear Physics in APS -2013 Fall Meeting - Event - Gravitational radiation theory http://meetings.aps.org/Meeting/DNP13/Session/FB.8, which I published, the gravity will br reduced to the original gravity percentage one. Waterspout by the Earth's gravity to become the original one percent. Cause the external of the tornadoes atmospheric pressure is constant, the height waterspout should support column height atmospheric pressure is 100 times,that height waterspout may reach nearly kilometers.

  14. Atmospheric pressure non-thermal plasma: Sources and applications

    NASA Astrophysics Data System (ADS)

    Napartovich, A. P.

    2008-07-01

    Non-thermal plasma at atmospheric pressure is an inherently unstable object. Nature of discharge plasma instabilities and conditions for observation of uniform non-thermal plasma at atmospheric pressure in different environments will be discussed. Various discharge techniques have been developed, which could support uniform non-thermal plasma with parameters varied in a wide range. Time limitation by plasma instabilities can be overcome by shortening pulse length or by restriction of plasma plug residence time with a fast gas flow. Discharge instabilities leading to formation of filaments or sparks are provoked by a positive feedback between the electric field and plasma density, while the counteracting process is plasma and thermal diffusion. With gas pressure growth the size of plasma fluctuation, which could be stabilized by diffusion, diminishes. As a result, to have long lived uniform plasma one should miniaturize discharge. There exist a number of active methods to organize negative feedback between the electric field and plasma density in order to suppress or, at least, delay the instability. Among them are ballast resistors in combination with electrode sectioning, reactive ballast, electronic feedback, and dielectric barrier across the electric current. The last methods are relevant for ac discharges. In the lecture an overview will be given of different discharge techniques scalable in pressure up to one atmosphere. The interest in this topic is dictated by a potential economic benefit from numerous non-thermal plasma technologies. The spectrum of non-thermal plasma applications is continuously broadening. An incomplete list of known applications includes: plasma-assisted chemical vapor deposition, etching, polymerization, gas-phase synthesis, protective coating deposition, toxic and harmful gas decomposition, destruction of warfare agents, electromagnetic wave shielding, polymer surface modifications, gas laser excitation, odor control, plasma assisted

  15. A flowing atmospheric pressure afterglow as an ion source coupled to a differential mobility analyzer for volatile organic compound detection.

    PubMed

    Bouza, Marcos; Orejas, Jaime; López-Vidal, Silvia; Pisonero, Jorge; Bordel, Nerea; Pereiro, Rosario; Sanz-Medel, Alfredo

    2016-05-23

    Atmospheric pressure glow discharges have been widely used in the last decade as ion sources in ambient mass spectrometry analyses. Here, an in-house flowing atmospheric pressure afterglow (FAPA) has been developed as an alternative ion source for differential mobility analysis (DMA). The discharge source parameters (inter-electrode distance, current and helium flow rate) determining the atmospheric plasma characteristics have been optimized in terms of DMA spectral simplicity with the highest achievable sensitivity while keeping an adequate plasma stability and so the FAPA working conditions finally selected were: 35 mA, 1 L min(-1) of He and an inter-electrode distance of 8 mm. Room temperature in the DMA proved to be adequate for the coupling and chemical analysis with the FAPA source. Positive and negative ions for different volatile organic compounds were tested and analysed by FAPA-DMA using a Faraday cup as a detector and proper operation in both modes was possible (without changes in FAPA operational parameters). The FAPA ionization source showed simpler ion mobility spectra with narrower peaks and a better, or similar, sensitivity than conventional UV-photoionization for DMA analysis in positive mode. Particularly, the negative mode proved to be a promising field of further research for the FAPA ion source coupled to ion mobility, clearly competitive with other more conventional plasmas such as corona discharge. PMID:27141552

  16. Nonlinear frequency coupling in dual radio-frequency driven atmospheric pressure plasmas

    SciTech Connect

    Waskoenig, J.; Gans, T.

    2010-05-03

    Plasma ionization, and associated mode transitions, in dual radio-frequency driven atmospheric pressure plasmas are governed through nonlinear frequency coupling in the dynamics of the plasma boundary sheath. Ionization in low-power mode is determined by the nonlinear coupling of electron heating and the momentary local plasma density. Ionization in high-power mode is driven by electron avalanches during phases of transient high electric fields within the boundary sheath. The transition between these distinctly different modes is controlled by the total voltage of both frequency components.

  17. Atmospheric Pressure Dielectric Barrier Discharges: A Low-Cost System for Surface Modification

    SciTech Connect

    Graz, I.; Schwoediauer, R.; Bauer, S.; Gruber, H.; Romanin, C.

    2005-10-17

    Plasma treatment is a common way for modifying the surface of a material. A simple but effective source for a low-temperature nonequilibrium plasma is dielectric barrier discharges (DBDs), also referred to as silent discharges. DBDs are characterized by the presence of at least one insulating (dielectric) layer in the discharge gap between two metal electrodes. When a high voltage is applied to the DBD configuration, tiny breakdown channels are formed in the discharge gap. These microdischarges are characterized as a weakly ionized plasma containing electrons with energies up to 10 eV and ions at room temperature. The energetic electrons provide an effective tool for chemical surface modification. Typical setups for DBD treatments consist of vacuum chambers and vacuum equipment, and so are very cost-intensive. Atmospheric pressure discharges provide a possibility for low-cost surface chemistry, because the setup consists only of the discharge set-up in normal air or in a specified inert gas atmosphere and a high-voltage amplifier coupled with a frequency generator. Silent discharges in air increase the wettability of polymer foils such as PTFE and FEP, sufficient for cell growth and further for surface-chemical binding of proteins onto the polymer. Thereby a simple and low-cost process to achieve protein chips for biomedical applications may be envisaged.

  18. Diagnostics of plasma-biological surface interactions in low pressure and atmospheric pressure plasmas

    NASA Astrophysics Data System (ADS)

    Ishikawa, Kenji; Hori, Masaru

    2014-08-01

    Mechanisms of plasma-surface interaction are required to understand in order to control the reactions precisely. Recent progress in atmospheric pressure plasma provides to apply as a tool of sterilization of contaminated foodstuffs. To use the plasma with safety and optimization, the real time in situ detection of free radicals - in particular dangling bonds by using the electron-spin-resonance (ESR) technique has been developed because the free radical plays important roles for dominantly biological reactions. First, the kinetic analysis of free radicals on biological specimens such as fungal spores of Penicillium digitatum interacted with atomic oxygen generated plasma electric discharge. We have obtained information that the in situ real time ESR signal from the spores was observed and assignable to semiquinone radical with a g-value of around 2.004 and a line width of approximately 5G. The decay of the signal was correlated with a link to the inactivation of the fungal spore. Second, we have studied to detect chemical modification of edible meat after the irradiation. Using matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF-MS) and ESR, signals give qualification results for chemical changes on edible liver meat. The in situ real-time measurements have proven to be a useful method to elucidate plasma-induced surface reactions on biological specimens.

  19. First steps towards the reaction kinetics of HMDSO in an atmospheric pressure plasma jet in argon

    NASA Astrophysics Data System (ADS)

    Loffhagen, Detlef; Becker, Markus M.; Foest, Rüdiger; Schäfer, Jan; Sigeneger, Florian

    2014-10-01

    Hexamethyldisiloxane (HMDSO) is a silicon-organic compound which is often used as precursor for thin-film deposition by means of plasma polymerization because of its high deposition rate and low toxicity. To improve the physical understanding of the deposition processes, fundamental investigations have been performed to clarify the plasma-chemical reaction pathways of HMDSO and their effect on the composition and structure of the deposited film. The current contribution represents the main primary and secondary plasma-chemical processes and their reaction products in the effluent region of an argon plasma jet at atmospheric pressure. The importance of the different collision processes of electrons and heavy particles are discussed. Results of numerical modelling of the plasma jet and the Ar-HMDSO reaction kinetics indicate that the fragmentation of HMDSO is mainly initiated by collisions with molecular argon ions, while Penning ionization processes play a minor role for the reaction kinetics in the effluent region of the jet. The work has been supported by the German Research Foundation (DFG) under Grant LO 623/3-1.

  20. Propagation of an atmospheric pressure plasma plume

    SciTech Connect

    Lu, X.; Xiong, Q.; Xiong, Z.; Hu, J.; Zhou, F.; Gong, W.; Xian, Y.; Zou, C.; Tang, Z.; Jiang, Z.; Pan, Y.

    2009-02-15

    The ''plasma bullet'' behavior of atmospheric pressure plasma plumes has recently attracted significant interest. In this paper, a specially designed plasma jet device is used to study this phenomenon. It is found that a helium primary plasma can propagate through the wall of a dielectric tube and keep propagating inside the dielectric tube (secondary plasma). High-speed photographs show that the primary plasma disappears before the secondary plasma starts to propagate. Both plumes propagate at a hypersonic speed. Detailed studies on the dynamics of the plasma plumes show that the local electric field induced by the charges on the surface of the dielectric tube plays an important role in the ignition of the secondary plasma. This indicates that the propagation of the plasma plumes may be attributed to the local electric field induced by the charges in the bulletlike plasma volume.

  1. Structure formation of atmospheric pressure discharge

    NASA Astrophysics Data System (ADS)

    Medvedev, Alexey E.

    2016-02-01

    In this paper it is shown, by analyzing the results of experimental studies, that the outer boundary of the atmospheric pressure discharge pinch is determined by the condition of equality of plasma flows based on the thermal and electric field energy. In most cases, the number of charged particles coming from near-electrode zones is sufficient to compensate for losses in the discharge bulk. At large currents and enhanced heating, plasma is in the diffusion mode of losses, with recombination of charged particles at the pinch boundary. Contribution to the Topical Issue "Recent Breakthroughs in Microplasma Science and Technology", edited by Kurt Becker, Jose Lopez, David Staack, Klaus-Dieter Weltmann and Wei Dong Zhu.

  2. Super-Atmospheric Pressure Ion Sources: Application and Coupling to API Mass Spectrometer

    PubMed Central

    Chen, Lee Chuin; Rahman, Md. Matiur; Hiraoka, Kenzo

    2014-01-01

    Pressurizing the ionization source to gas pressure greater than atmospheric pressure is a new tactic aimed at further improving the performance of atmospheric pressure ionization (API) sources. In principle, all API sources, such as ESI, APCI and AP-MALDI, can be operated at pressure higher than 1 atm if suitable vacuum interface is available. The gas pressure in the ion source can have different role for different ionization. For example, in the case of ESI, stable electrospray could be sustained for high surface tension liquid (e.g., pure water) under super-atmospheric pressure, owing to the absence of electric discharge. Even for nanoESI, which is known to work well with aqueous solution, its stability and sensitivity were found to be enhanced, particularly in the negative mode when the ion source was pressurized. For the gas phase ionization like APCI, measurement of gaseous compound also showed an increase in ion intensity with the ion source pressure until an optimum pressure at around 4–5 atm. The enhancement was due to the increased collision frequency among reactant ion and analyte that promoted the ion/molecule reaction and a higher intake rate of gas to the mass spectrometer. Because the design of vacuum interface for API instrument is based on the upstream pressure of 1 atm, some coupling aspects need to be considered when connecting the high pressure ion source to the mass spectrometer. Several coupling strategies are discussed in this paper. PMID:26819896

  3. Helium atmospheric pressure plasma jets touching dielectric and metal surfaces

    NASA Astrophysics Data System (ADS)

    Norberg, Seth A.; Johnsen, Eric; Kushner, Mark J.

    2015-07-01

    Atmospheric pressure plasma jets (APPJs) are being investigated in the context plasma medicine and biotechnology applications, and surface functionalization. The composition of the surface being treated ranges from plastics, liquids, and biological tissue, to metals. The dielectric constant of these materials ranges from as low as 1.5 for plastics to near 80 for liquids, and essentially infinite for metals. The electrical properties of the surface are not independent variables as the permittivity of the material being treated has an effect on the dynamics of the incident APPJ. In this paper, results are discussed from a computational investigation of the interaction of an APPJ incident onto materials of varying permittivity, and their impact on the discharge dynamics of the plasma jet. The computer model used in this investigation solves Poisson's equation, transport equations for charged and neutral species, the electron energy equation, and the Navier-Stokes equations for the neutral gas flow. The APPJ is sustained in He/O2 = 99.8/0.2 flowing into humid air, and is directed onto dielectric surfaces in contact with ground with dielectric constants ranging from 2 to 80, and a grounded metal surface. Low values of relative permittivity encourage propagation of the electric field into the treated material and formation and propagation of a surface ionization wave. High values of relative permittivity promote the restrike of the ionization wave and the formation of a conduction channel between the plasma discharge and the treated surface. The distribution of space charge surrounding the APPJ is discussed.

  4. Atmospheric pressure photoionization mass spectrometry as a tool for the investigation of the hydrolysis reaction mechanisms of phosphite antioxidants

    NASA Astrophysics Data System (ADS)

    Papanastasiou, M.; McMahon, A. W.; Allen, N. S.; Johnson, B. W.; Keck-Antoine, K.; Santos, L.; Neumann, M. G.

    2008-08-01

    The hydrolysis reaction mechanism of phosphite antioxidants is investigated by liquid chromatography-mass spectrometry (LC/MS). The phosphites were chosen because they differed in chemical structure and phosphorus content. Dopant assisted-atmospheric pressure photoionization (DA-APPI) is chosen as the ion source for the ionization of the compounds. In our previous work, DA-APPI was shown to offer an attractive alternative to atmospheric pressure chemical ionization (APCI) since it provided background-ion free mass spectra and higher sensitivity [M. Papanastasiou, et al., Polymer Degradation and Stability 91 (11) (2006) 2675-2682]. In positive ion mode, the molecules are generally detected in their protonated form. In negative ion mode, the phosphites are unstable and only fragment ions are observed; these however, are characteristic of each phosphite and may be used for the identification of the analytes in complex mixtures. The analytes under investigation are exposed to accelerated humid ageing conditions and their hydrolytic pathway and stability is investigated. Different substituents around the phosphorus atom are shown to have a significant effect on the stability of the phosphites, with phenol substituents producing very hydrolytically stable structures. Alkanox P24 and PEP-36 follow a similar hydrolytic pathway via the scission of the first and then the second POphenol bonds, eventually leading to the formation of phenol, phosphorous acid and pentaerythritol as end products. HP-10 exhibits a rather different structure and the products detected suggest scission of either the POhydrocarbon or one of the POphenol bonds. A phenomenon similar to that of autocatalysis is observed for all phosphites and is attributed to the formation of dialkyl phosphites as intermediate products.

  5. Direct Analysis of Nonvolatile Chemical Compounds on Surfaces Using a Hand-Held Mass Spectrometer with Synchronized Discharge Ionization Function.

    PubMed

    Wang, Xiao; Zhou, Xiaoyu; Ouyang, Zheng

    2016-01-01

    Synchronized discharge ionization (SDI) was previously developed for hand-held mass spectrometers with discontinuous atmospheric pressure interfaces. The function of SDI has been demonstrated for analysis of volatile organic compounds in air at high sensitivity, which is attributed to the fact that ions were produced next to the ion trap mass analyzer inside the vacuum manifold. In this study, a simple sampling device was designed and fitted to a hand-held mass spectrometer to characterize its potential in direct analysis of low-volatility chemicals on surfaces. Nine chemicals of vapor pressures ranging from 10(-4) to 10(-8) Torr (at room temperature), including pesticides, illicit drugs, and explosives, were selected to evaluate and demonstrate the analytical capability of the designed system. Compounds of vapor pressures below 10(-7) Torr, such as tetryl, cocaine, and tetrahydrocannabinol (THC), have been successfully detected. Direct analysis of pesticides from fruit and explosives from a large surface area has also been demonstrated. Tandem mass analysis was performed, which helped to confirm the analyte identity as well as to improve the signal-to-noise ratio (S/N). PMID:26618852

  6. Numerical simulations of superlattice patterns in dielectric barrier discharges at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Liu, Fucheng; Wang, Xiaofei; He, Yafeng; Dong, Lifang

    2016-03-01

    This paper presents the numerical investigation on superlattice patterns in atmospheric pressure glow discharges in dielectric barrier discharges by using a self-consistent 2D fluid model. It is found that the superlattice pattern is an interleaving of two filamentary sub-patterns with alternate spatial and temporal characteristics. The competition between the volume ionization and the memory effects of both surface charges and space charges is expected to the formation mechanism of this superlattice pattern.

  7. Sterilization of Surfaces with a Handheld Atmospheric Pressure Plasma

    NASA Astrophysics Data System (ADS)

    Hicks, Robert; Habib, Sara; Chan, Wai; Gonzalez, Eleazar; Tijerina, A.; Sloan, Mark

    2009-10-01

    Low temperature, atmospheric pressure plasmas have shown great promise for decontaminating the surfaces of materials and equipment. In this study, an atmospheric pressure, oxygen and argon plasma was investigated for the destruction of viruses, bacteria, and spores. The plasma was operated at an argon flow rate of 30 L/min, an oxygen flow rate of 20 mL/min, a power density of 101.0 W/cm^3 (beam area = 5.1 cm^2), and at a distance from the surface of 7.1 mm. An average 6log10 reduction of viable spores was obtained after only 45 seconds of exposure to the reactive gas. By contrast, it takes more than 35 minutes at 121^oC to sterilize anthrax in an autoclave. The plasma properties were investigated by numerical modeling and chemical titration with nitric oxide. The numerical model included a detailed reaction mechanism for the discharge as well as for the afterglow. It was predicted that at a delivered power density of 29.3 W/cm^3, 30 L/min argon, and 0.01 volume% O2, the plasma generated 1.9 x 10^14 cm-3 O atoms, 1.6 x 10^12 cm-3 ozone, 9.3 x 10^13 cm-3 O2(^1δg), and 2.9 x 10^12 cm-3 O2(^1σ^+g) at 1 cm downstream of the source. The O atom density measured by chemical titration with NO was 6.0 x 10^14 cm-3 at the same conditions. It is believe that the oxygen atoms and the O2(^1δg) metastables were responsible for killing the anthrax and other microorganisms.

  8. Effect of Atmospheric Pressure Plasma Modification on Polyimide and Adhesive Joining with Titanium

    NASA Astrophysics Data System (ADS)

    Akram, M.; Jansen, K. M. B.; Ernst, L. J.; Bhowmik, S.; Ajeesh, G.; Ahmed, S.; Chakraborty, D.

    2015-10-01

    This investigation highlights the effect of surface modification on polyimide by atmospheric pressure plasma treatment with different exposure time. Surface modification of polymer by plasma treatment essentially creates physical and chemical changes such as cross-linking and formation of free radicals. It also forms oxygen functionalization in the form of polar groups on polymer surface, hence improving the wetting and adhesion properties. It is observed that surface energy of the polymer increases with increasing exposure time of atmospheric pressure plasma. However, prolonged exposure time of plasma results in deterioration of the surface layer of polyimide resulting in degradation and embrittlement. Scanning electron microscopy and atomic force microscopy analysis reveal that there is a considerable morphological change on the polymer surface due to atmospheric pressure plasma treatment. X-ray photo electron spectroscopy analysis reveals that the oxygen functionalities of polymer surface increases significantly when polyimide is exposed to atmospheric pressure plasma. Untreated and atmospheric pressure plasma-treated polyimide sheet are adhesive bonded by employing polyimide adhesive as well as with titanium substrate. Due to surface modification of polyimide, it is observed that there is a significant increase in lap shear tensile strength, and therefore, this technology is highly acceptable for aviation and space applications.

  9. Design and performance of an atmospheric pressure inlet system for lithium ion attachment mass spectrometry.

    PubMed

    Selvin, P Christopher; Iwase, Keiichiro; Fujii, Toshihiro

    2002-05-01

    We designed a simple and efficient inlet system to act as an interface between samples at atmospheric pressure and the high vacuum inside a mass spectrometer. The newly designed stainless steel orifice leak sample inlet system is simple and rugged and fulfills all the basic requirements. With this inlet system coupled with a lithium ion attachment mass spectrometer, it is possible to detect any chemical species at atmospheric pressure, including radical intermediates, on a real-time basis. For illustrative purposes, the sampling efficiency of the inlet probe coupled with a lithium ion attachment mass spectrometer is discussed for laboratory air and polyethylene pyrolysis. PMID:12033306

  10. A computational modeling study on the helium atmospheric pressure plasma needle discharge

    NASA Astrophysics Data System (ADS)

    Qian, Mu-Yang; Yang, Cong-Ying; Liu, San-Qiu; Wang, Zhen-Dong; Lv, Yan; Wang, De-Zhen

    2015-12-01

    A two-dimensional coupled model of neutral gas flow and plasma dynamics is employed to investigate the streamer dynamics in a helium plasma needle at atmospheric pressure. A parametric study of the streamer propagation as a function of needle tip curvature radius and helium gas flow rate is presented. The key chemical reactions at the He/air mixing layer which drive the streamer propagation are the direct ionization via collision with electrons, the Penning effect being not so crucial. With increasing the gas flow rate from 0.2 standard liter per minute (SLM) to 0.8 SLM, however, the emissions resulting from reactive oxygen and nitrogen species change from a solid circle to a hollow profile and the average streamer propagation velocity decreases. Air impurities (backdiffusion from ambient air) in the helium jet result in a significant increase in the streamer propagation velocity. Besides, with decreasing the tip curvature radiusfrom 200 μm to 100 μm, the electron avalanche process around the near-tip region is more pronounced. However, the spatially resolved plasma parameters distributions (electron, helium metastables, ground state atomic oxygen, etc.) remain almost the same, except that around the near-tip region where their peak values are more than doubled. Project supported partly by the National Natural Science Foundation of China (Grant No. 11465013), the Natural Science Foundation of Jiangxi Province, China (Grant No. 20151BAB212012), and in part by the International Science and Technology Cooperation Program of China (Grant No. 2015DFA61800).

  11. Response of cyanobacteria to low atmosphere pressure

    NASA Astrophysics Data System (ADS)

    Qin, Lifeng; Ai, Weidang; Guo, Shuangsheng; Tang, Yongkang; Yu, Qingni; Shen, Yunze; Ren, Jin

    Maintaining a low pressure environment would reduce the technological complexity and constructed cost of future lunar base. To estimate the effect of hypobaric of controlled ecological life support system in lunar base on terrestrial life, cyanobacteria was used as the model to exam the response of growth, morphology, physiology to it. The decrease of atmosphere pressure from 100 KPa to 50 KPa reducing the growth rates of Microcystis aeruginosa, Merismopedia.sp, Anabaena sp. PCC 7120, Anabaena Hos-aquae, the chlorophyll a content in Microcystis aeruginosa, Merismopedia.sp, Anabaena Hos-aquae, the carotenoid content in Microcystis aeruginosa, Merismopedia.sp and Anabaena sp. PCC 7120, the phycocyanin content in Microcystis aeruginosa. This study explored the biological characteristics of the cyanobacteria under low pressure condition, which aimed at understanding the response of the earth's life to environment for the future moon base, the results enrich the research contents of the lunar biology and may be referred for the research of other terrestrial life, such as human, plant, microbe and animal living in life support system of lunar base.

  12. Three Modes of Air Atmospheric Pressure Plasma

    NASA Astrophysics Data System (ADS)

    Mohamed, Abdel-Aleam H.

    2015-09-01

    Atmospheric pressure plasma jet operating in air have gained a high interest due to its various applications in industry and biomedical. The presented air plasma jet system is consisted of stainless steel hollow needle electrode of 1 mm inner diameter which is covered with a quartz tube with a 1 mm diameter side hole. The hole is above the tube nozzle by 5 mm and it is covered by a copper ring which is connected to the ground. The needle is connected to sinusoidal 27 kHz high voltage power supply (25 kV) though a current limiting resistor of 50 k Ω. The tested distance between the needle tip and the side hole was 1 mm or 2.1 mm gape. The electric and plasma jet formation characteristics show three modes of operations. Through these modes the plasma length changes with air flow rate to increase in the first mode and to confine inside the quartz tube in the second mode, then it start to eject from the nozzle again and increase with flow rate to reach a maximum length of 7 mm at 4.5 SLM air flow rate in the third mode. The measured gas temperature of the plasma jet can approach room temperature (300 K). Moreover, the plasma jet emission spectra shows the presence of reactive O and OH radical in the plasma jet. These results indicate that the generated air plasma jet can be used a plasma sterilization.

  13. Generation and control of wide area, homogenous atmospheric pressure discharges for industrial coating applications.

    NASA Astrophysics Data System (ADS)

    Hynes, Alan; Walter, Castagna; Carr, Kieran; O'Shea, Sean; Herbert, Tony

    2004-09-01

    Dow Corning Plasma Solutions use diffuse atmospheric pressure plasma technology combined with a unique precursor delivery system for a new coatings approach: Atmospheric Pressure Plasma Liquid Deposition. Operating at atmospheric pressure and ambient temperature this process allows the use of a wide range of liquid precursors delivering high chemical functionality onto flexible substrates. Patented APPLD equipment enables plasma deposition onto wide area substrates up to 1.6m width in true reel-to-reel conditions at industrial line speeds up to 30m/min. Substrates can be either electrically insulating or conducting. Recent engineering developments addressing issues in electrode design, liquid delivery and gas retention and distribution, have significantly enhanced the stability and homogeneity of the plasma chemistry and coating performance. The process is controlled through monitoring and control of key plasma chemistry and process parameters. The process hardware and process control package will be described in detail with particular emphasis on plasma chemistry and process control tools.

  14. 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

  15. Atmospheric pressure arc discharge with ablating graphite anode

    SciTech Connect

    Nemchinsky, V. A.; Raitses, Y.

    2015-05-18

    The anodic carbon arc discharge is used to produce carbon nanoparticles. Recent experiments with the carbon arc at atmospheric pressure helium demonstrated the enhanced ablation rate for narrow graphite anodes resulting in high deposition rates of carbonaceous products on the copper cathode (Fetterman et al 2008 Carbon 46 1322–6). The proposed model explains these results with interconnected steady-state models of the cathode and the anode processes. When considering cathode functioning, the model predicts circulation of the particles in the near-cathode region: evaporation of the cathode material, ionization of evaporated atoms and molecules in the near-cathode plasma, return of the resulting ions to the cathode, surface recombination of ions and electrons followed again by cathode evaporation etc. In the case of the low anode ablation rate, the ion acceleration in the cathode sheath provides the major cathode heating mechanism. In the case of an intensive anode ablation, an additional cathode heating is due to latent fusion heat of the atomic species evaporated from the anode and depositing at the cathode. Using the experimental arc voltage as the only input discharge parameter, the model allows us to calculate the anode ablation rate. A comparison of the results of calculations with the available experimental data shows reasonable agreement.

  16. Dynamics behavior of homogeneous dielectric barrier discharge at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Zhang, Yan; Gu, Biao; Wang, Wenchun; Wang, Dezhen; Peng, Xuwen

    2009-07-01

    An experimental study on the dynamics behavior of homogeneous dielectric barrier discharge (HDBD) at atmospheric pressure is described in this paper. Two kinds of discharge mode, glow and Townsend discharge modes, can be easily identified according to the differential conductivity of current-voltage relationship in the ascent stage of discharge current for the atmospheric HDBD. A (three-dimensional) 3D phase space made by discharge current, gas gap voltage, and charge density of dielectric-plate surface was utilized in the study. By projecting the discharge evolution trajectory in the 3D space, the 3D trajectory of multiple current peaks discharge in atmospheric helium shows a limited cycle with convolutions and undergoes a series of bifurcation process; however, the 3D trajectory of atmospheric N2 HDBD is a limited cycle without any convolution and bifurcation process. In addition, the first ionization coefficient of working gas plays a key role to determine the discharge mode of atmospheric HDBD, the transition of discharge mode and the dynamics stability of atmospheric HDBD.

  17. Dynamics behavior of homogeneous dielectric barrier discharge at atmospheric pressure

    SciTech Connect

    Zhang Yan; Gu Biao; Wang Wenchun; Wang Dezhen; Peng Xuwen

    2009-07-15

    An experimental study on the dynamics behavior of homogeneous dielectric barrier discharge (HDBD) at atmospheric pressure is described in this paper. Two kinds of discharge mode, glow and Townsend discharge modes, can be easily identified according to the differential conductivity of current-voltage relationship in the ascent stage of discharge current for the atmospheric HDBD. A (three-dimensional) 3D phase space made by discharge current, gas gap voltage, and charge density of dielectric-plate surface was utilized in the study. By projecting the discharge evolution trajectory in the 3D space, the 3D trajectory of multiple current peaks discharge in atmospheric helium shows a limited cycle with convolutions and undergoes a series of bifurcation process; however, the 3D trajectory of atmospheric N{sub 2} HDBD is a limited cycle without any convolution and bifurcation process. In addition, the first ionization coefficient of working gas plays a key role to determine the discharge mode of atmospheric HDBD, the transition of discharge mode and the dynamics stability of atmospheric HDBD.

  18. Radiative ion-ion neutralization: a new gas-phase atmospheric pressure ion transduction mechanism.

    PubMed

    Davis, Eric J; Siems, William F; Hill, Herbert H

    2012-06-01

    All atmospheric pressure ion detectors, including photo ionization detectors, flame ionization detectors, electron capture detectors, and ion mobility spectrometers, utilize Faraday plate designs in which ionic charge is collected and amplified. The sensitivity of these Faraday plate ion detectors are limited by thermal (Johnson) noise in the associated electronics. Thus approximately 10(6) ions per second are required for a minimal detection. This is not the case for ion detection under vacuum conditions where secondary electron multipliers (SEMs) can be used. SEMs produce a cascade of approximately 10(6) electrons per ion impinging on the conversion dynode. Similarly, photomultiplier tubes (PMTs) can generate approximately 10(6) electrons per photon. Unlike SEMs, however, PMTs are evacuated and sealed so that they are commonly used under atmospheric pressure conditions. This paper describes an atmospheric pressure ion detector based on coupling a PMT with light emitted from ion-ion neutralization reactions. The normal Faraday plate collector electrode was replaced with an electrode "needle" used to concentrate the anions as they were drawn to the tip of the needle by a strong focusing electric field. Light was emitted near the surface of the electrode when analyte ions were neutralized with cations produced from the anode. Although radiative-ion-ion recombination has been previously reported, this is the first time ions from separate ionization sources have been combined to produce light. The light from this radiative-ion-ion-neutralization (RIIN) was detected using a photon multiplier such that an ion mobility spectrum was obtained by monitoring the light emitted from mobility separated ions. An IMS spectrum of nitroglycerin (NG) was obtained utilizing RIIN for tranducing the mobility separated ions into an analytical signal. The implications of this novel ion transduction method are the potential for counting ions at atmospheric pressure and for obtaining ion

  19. Cold plasma brush generated at atmospheric pressure

    SciTech Connect

    Duan Yixiang; Huang, C.; Yu, Q. S.

    2007-01-15

    A cold plasma brush is generated at atmospheric pressure with low power consumption in the level of several watts (as low as 4 W) up to tens of watts (up to 45 W). The plasma can be ignited and sustained in both continuous and pulsed modes with different plasma gases such as argon or helium, but argon was selected as a primary gas for use in this work. The brush-shaped plasma is formed and extended outside of the discharge chamber with typical dimension of 10-15 mm in width and less than 1.0 mm in thickness, which are adjustable by changing the discharge chamber design and operating conditions. The brush-shaped plasma provides some unique features and distinct nonequilibrium plasma characteristics. Temperature measurements using a thermocouple thermometer showed that the gas phase temperatures of the plasma brush are close to room temperature (as low as 42 deg. C) when running with a relatively high gas flow rate of about 3500 ml/min. For an argon plasma brush, the operating voltage from less than 500 V to about 2500 V was tested, with an argon gas flow rate varied from less than 1000 to 3500 ml/min. The cold plasma brush can most efficiently use the discharge power as well as the plasma gas for material and surface treatment. The very low power consumption of such an atmospheric argon plasma brush provides many unique advantages in practical applications including battery-powered operation and use in large-scale applications. Several polymer film samples were tested for surface treatment with the newly developed device, and successful changes of the wettability property from hydrophobic to hydrophilic were achieved within a few seconds.

  20. Quantification of hydroxyacetone and glycolaldehyde using chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Spencer, K. M.; Beaver, M. R.; St. Clair, J. M.; Crounse, J. D.; Paulot, F.; Wennberg, P. O.

    2011-08-01

    Chemical ionization mass spectrometry (CIMS) enables online, fast, in situ detection and quantification of hydroxyacetone and glycolaldehyde. Two different CIMS approaches are demonstrated employing the strengths of single quadrupole mass spectrometry and triple quadrupole (tandem) mass spectrometry. Both methods are capable of the measurement of hydroxyacetone, an analyte with minimal isobaric interferences. Tandem mass spectrometry provides direct separation of the isobaric compounds glycolaldehyde and acetic acid using distinct, collision-induced dissociation daughter ions. Measurement of hydroxyacetone and glycolaldehyde by these methods was demonstrated during the ARCTAS-CARB 2008 campaign and the BEARPEX 2009 campaign. Enhancement ratios of these compounds in ambient biomass burning plumes are reported for the ARCTAS-CARB campaign. BEARPEX observations are compared to simple photochemical box model predictions of biogenic volatile organic compound oxidation at the site.

  1. Characterization of glycosphingolipids by direct inlet chemical ionization mass spectrometry.

    PubMed

    Ariga, T; Murata, T; Oshima, M; Maezawa, M; Miyatake, T

    1980-09-01

    Permethylated derivatives of cerebrosides and ceramide di-, tri-, tetra-, and penta-hexosides were analyzed by the direct inlet ammonia chemical ionization (CI) mass spectrometry. In the CI mass spectra, the fragment ions produced by the loss of methanol from the protonated molecular ion were observed in all of the glycosphingolipids. Other fragment ions due to the cleavage of glycosidic moiety were major ones under the CI conditions. These ions provide information on the molecular species of glycosphingolipids and the sugar sequence of their oligosaccharides. Glycosphingolipids with hydroxy fatty acids could also be differentiated from those with nonhydroxy fatty acids by comparing the intensities of characteristic fragment ions. The CI method should be particularly useful in structural studies of glycosphingolipids from natural sources. PMID:7441059

  2. Analytical model of atmospheric pressure, helium/trace gas radio-frequency capacitive Penning discharges

    NASA Astrophysics Data System (ADS)

    Lieberman, M. A.

    2015-04-01

    Atmospheric and near-atmospheric pressure, helium/trace gas radio-frequency capacitive discharges have wide applications. An analytic equilibrium solution is developed based on a homogeneous, current-driven discharge model that includes sheath and electron multiplication effects and contains two electron populations. A simplified chemistry is used with four unknown densities: hot electrons, warm electrons, positive ions and metastables. The dominant electron-ion pair production is Penning ionization, and the dominant ion losses are to the walls. The equilibrium particle balances are used to determine a single ionization balance equation for the warm electron temperature, which is solved, both approximately within the α- and γ-modes, and exactly by conventional root-finding techniques. All other discharge parameters are found, the extinction and α-γ transitions are determined, and a similarity law is given, in which the equilibrium for a short gap at high pressure can be rescaled to a longer gap at lower pressure. Within the α-mode, we find the scaling of the discharge parameters with current density, frequency, gas density and gap width. The analytic results are compared to hybrid and particle-in-cell (PIC) results for He/0.1%N2, and to hybrid results for He/0.1%H2O. For nitrogen, a full reaction set is used for the hybrid calculations and a simplified reaction set for the PIC simulations. For the chemically complex water trace gas, a set of 209 reactions among 43 species is used. The analytic results are found to be in reasonably good agreement with the more elaborate hybrid and PIC calculations.

  3. Helium atmospheric pressure plasma jets touching dielectric and metal surfaces

    SciTech Connect

    Norberg, Seth A. Johnsen, Eric; Kushner, Mark J.

    2015-07-07

    Atmospheric pressure plasma jets (APPJs) are being investigated in the context plasma medicine and biotechnology applications, and surface functionalization. The composition of the surface being treated ranges from plastics, liquids, and biological tissue, to metals. The dielectric constant of these materials ranges from as low as 1.5 for plastics to near 80 for liquids, and essentially infinite for metals. The electrical properties of the surface are not independent variables as the permittivity of the material being treated has an effect on the dynamics of the incident APPJ. In this paper, results are discussed from a computational investigation of the interaction of an APPJ incident onto materials of varying permittivity, and their impact on the discharge dynamics of the plasma jet. The computer model used in this investigation solves Poisson's equation, transport equations for charged and neutral species, the electron energy equation, and the Navier-Stokes equations for the neutral gas flow. The APPJ is sustained in He/O{sub 2} = 99.8/0.2 flowing into humid air, and is directed onto dielectric surfaces in contact with ground with dielectric constants ranging from 2 to 80, and a grounded metal surface. Low values of relative permittivity encourage propagation of the electric field into the treated material and formation and propagation of a surface ionization wave. High values of relative permittivity promote the restrike of the ionization wave and the formation of a conduction channel between the plasma discharge and the treated surface. The distribution of space charge surrounding the APPJ is discussed.

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

    NASA Astrophysics Data System (ADS)

    Spencer, Kathleen M.

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

  5. Reactivity zones around an atmospheric pressure plasma jet

    NASA Astrophysics Data System (ADS)

    Birer, Özgür

    2015-11-01

    The reactivity zones around an atmospheric pressure plasma jet are revealed by XPS mapping of chemical moieties on a polyethylene surface treated with a 3-mm plasma jet. The area directly hit by the helium plasma jet initially oxidizes and later etches away as the plasma treatment continues. The oxidation initially starts at the center and expands outwards as a ring pattern with different spatial potency. At the end of 10 min plasma jet treatment, distinct ring patterns for -NO, -COO, -CO and -NO3 species can be detected with respectively increasing diameters. The plasma jet can cause chemical changes at locations several millimeters away from the center. The spatial distribution of oxidized species suggests presence of chemical reactivity zones. Introduction of nitrogen into the helium plasma jet, not only increases the type of nitrogen moieties, but enriches the reactivity zones by generating nitrogen molecular ions within the plasma jet. The complex competing reaction mechanisms among the radicals, ions, metastable atoms and UV photons lead to unusual etching patterns on the surfaces.

  6. Comparison of direct and alternating current vacuum ultraviolet lamps in atmospheric pressure photoionization.

    PubMed

    Vaikkinen, Anu; Haapala, Markus; Kersten, Hendrik; Benter, Thorsten; Kostiainen, Risto; Kauppila, Tiina J

    2012-02-01

    A direct current induced vacuum ultraviolet (dc-VUV) krypton discharge lamp and an alternating current, radio frequency (rf) induced VUV lamp that are essentially similar to lamps in commercial atmospheric pressure photoionization (APPI) ion sources were compared. The emission distributions along the diameter of the lamp exit window were measured, and they showed that the beam of the rf lamp is much wider than that of the dc lamp. Thus, the rf lamp has larger efficient ionization area, and it also emits more photons than the dc lamp. The ionization efficiencies of the lamps were compared using identical spray geometries with both lamps in microchip APPI mass spectrometry (μAPPI-MS) and desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS). A comprehensive view on the ionization was gained by studying six different μAPPI solvent compositions, five DAPPI spray solvents, and completely solvent-free DAPPI. The observed reactant ions for each solvent composition were very similar with both lamps except for toluene, which showed a higher amount of solvent originating oxidation products with the rf lamp than with the dc lamp in μAPPI. Moreover, the same analyte ions were detected with both lamps, and thus, the ionization mechanisms with both lamps are similar. The rf lamp showed a higher ionization efficiency than the dc lamp in all experiments. The difference between the lamp ionization efficiencies was greatest when high ionization energy (IE) solvent compositions (IEs above 10 eV), i.e., hexane, methanol, and methanol/water, (1:1 v:v) were used. The higher ionization efficiency of the rf lamp is likely due to the larger area of high intensity light emission, and the resulting larger efficient ionization area and higher amount of photons emitted. These result in higher solvent reactant ion production, which in turn enables more efficient analyte ion production. PMID:22229729

  7. Atmospheric pressure plasma jet with high-voltage power supply based on piezoelectric transformer

    SciTech Connect

    Babij, Michał; Kowalski, Zbigniew W. Nitsch, Karol; Gotszalk, Teodor; Silberring, Jerzy

    2014-05-15

    The dielectric barrier discharge plasma jet, an example of the nonthermal atmospheric pressure plasma jet (APPJ), generates low-temperature plasmas that are suitable for the atomization of volatile species and can also be served as an ionization source for ambient mass and ion mobility spectrometry. A new design of APPJ for mass spectrometry has been built in our group. In these plasma sources magnetic transformers (MTs) and inductors are typically used in power supplies but they present several drawbacks that are even more evident when dealing with high-voltage normally used in APPJs. To overcome these disadvantages, high frequency generators with the absence of MT are proposed in the literature. However, in the case of miniaturized APPJs these conventional power converters, built of ferromagnetic cores and inductors or by means of LC resonant tank circuits, are not so useful as piezoelectric transformer (PT) based power converters due to bulky components and small efficiency. We made and examined a novel atmospheric pressure plasma jet with PT supplier served as ionization source for ambient mass spectrometry, and especially mobile spectrometry where miniaturization, integration of components, and clean plasma are required. The objective of this paper is to describe the concept, design, and implementation of this miniaturized piezoelectric transformer-based atmospheric pressure plasma jet.

  8. Atmospheric pressure plasma jet with high-voltage power supply based on piezoelectric transformer.

    PubMed

    Babij, Michał; Kowalski, Zbigniew W; Nitsch, Karol; Silberring, Jerzy; Gotszalk, Teodor

    2014-05-01

    The dielectric barrier discharge plasma jet, an example of the nonthermal atmospheric pressure plasma jet (APPJ), generates low-temperature plasmas that are suitable for the atomization of volatile species and can also be served as an ionization source for ambient mass and ion mobility spectrometry. A new design of APPJ for mass spectrometry has been built in our group. In these plasma sources magnetic transformers (MTs) and inductors are typically used in power supplies but they present several drawbacks that are even more evident when dealing with high-voltage normally used in APPJs. To overcome these disadvantages, high frequency generators with the absence of MT are proposed in the literature. However, in the case of miniaturized APPJs these conventional power converters, built of ferromagnetic cores and inductors or by means of LC resonant tank circuits, are not so useful as piezoelectric transformer (PT) based power converters due to bulky components and small efficiency. We made and examined a novel atmospheric pressure plasma jet with PT supplier served as ionization source for ambient mass spectrometry, and especially mobile spectrometry where miniaturization, integration of components, and clean plasma are required. The objective of this paper is to describe the concept, design, and implementation of this miniaturized piezoelectric transformer-based atmospheric pressure plasma jet. PMID:24880391

  9. 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.

  10. Deposition of Functional Coatings from an Acetylene-Containing Plasma at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Plevako, F. V.; Gorbatov, S. V.; Davidovich, P. A.; Prikhod‧ko, E. M.; Shushkov, S. V.; Krul‧, L. P.; Butovskaya, G. V.; Shakhno, O. V.; Gusakova, S. V.; Korolik, O. V.; Mazanik, A. V.

    2016-03-01

    Properties of thin coatings formed on polymer and glass substrates by plasma-enhanced chemical vapor deposition from a mixture of nitrogen with acetylene at atmospheric pressure were investigated. It was established that chemically stable transparent films with a mass ratio of fixed carbon and nitrogen C:N ~ 2:1 are formed on the surface of these substrates. When the deposition time was increased, arrays of dendrite-like structures were formed on the substrates.

  11. Using atmospheric pressure plasma treatment for treating grey cotton fabric.

    PubMed

    Kan, Chi-Wai; Lam, Chui-Fung; Chan, Chee-Kooi; Ng, Sun-Pui

    2014-02-15

    Conventional wet treatment, desizing, scouring and bleaching, for grey cotton fabric involves the use of high water, chemical and energy consumption which may not be considered as a clean process. This study aims to investigate the efficiency of the atmospheric pressure plasma (APP) treatment on treating grey cotton fabric when compared with the conventional wet treatment. Grey cotton fabrics were treated with different combinations of plasma parameters with helium and oxygen gases and also through conventional desizing, scouring and bleaching processes in order to obtain comparable results. The results obtained from wicking and water drop tests showed that wettability of grey cotton fabrics was greatly improved after plasma treatment and yielded better results than conventional desizing and scouring. The weight reduction of plasma treated grey cotton fabrics revealed that plasma treatment can help remove sizing materials and impurities. Chemical and morphological changes in plasma treated samples were analysed by FTIR and SEM, respectively. Finally, dyeability of the plasma treated and conventional wet treated grey cotton fabrics was compared and the results showed that similar dyeing results were obtained. This can prove that plasma treatment would be another choice for treating grey cotton fabrics. PMID:24507269

  12. Characteristics of Atmospheric Pressure Rotating Gliding Arc Plasmas

    NASA Astrophysics Data System (ADS)

    Zhang, Hao; Zhu, Fengsen; Tu, Xin; Bo, Zheng; Cen, Kefa; Li, Xiaodong

    2016-05-01

    In this work, a novel direct current (DC) atmospheric pressure rotating gliding arc (RGA) plasma reactor has been developed for plasma-assisted chemical reactions. The influence of the gas composition and the gas flow rate on the arc dynamic behaviour and the formation of reactive species in the N2 and air gliding arc plasmas has been investigated by means of electrical signals, high speed photography, and optical emission spectroscopic diagnostics. Compared to conventional gliding arc reactors with knife-shaped electrodes which generally require a high flow rate (e.g., 10–20 L/min) to maintain a long arc length and reasonable plasma discharge zone, in this RGA system, a lower gas flow rate (e.g., 2 L/min) can also generate a larger effective plasma reaction zone with a longer arc length for chemical reactions. Two different motion patterns can be clearly observed in the N2 and air RGA plasmas. The time-resolved arc voltage signals show that three different arc dynamic modes, the arc restrike mode, takeover mode, and combined modes, can be clearly identified in the RGA plasmas. The occurrence of different motion and arc dynamic modes is strongly dependent on the composition of the working gas and gas flow rate. supported by National Natural Science Foundation of China (No. 51576174), the Specialized Research Fund for the Doctoral Program of Higher Education of China (No. 20120101110099) and the Fundamental Research Funds for the Central Universities (No. 2015FZA4011)

  13. Chemical Aspects of the Extractive Methods of Ambient Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Badu-Tawiah, Abraham K.; Eberlin, Livia S.; Ouyang, Zheng; Cooks, R. Graham

    2013-04-01

    Ambient ionization techniques allow complex chemical samples to be analyzed in their native state with minimal sample preparation. This brings the obvious advantages of simplicity, speed, and versatility to mass spectrometry: Desorption electrospray ionization (DESI), for example, is used in chemical imaging for tumor margin diagnosis. This review on the extractive methods of ambient ionization focuses on chemical aspects, mechanistic considerations, and the accelerated chemical reactions occurring in charged liquid droplets generated in the spray process. DESI uses high-velocity solvent droplets to extract analytes from surfaces. Nano-DESI employs liquid microjunctions for analyte dissolution, whereas paper-spray ionization uses DC potentials applied to wet porous material such as paper or biological tissue to field emit charged analyte-containing solvent droplets. These methods also operate in a reactive mode in which added reagents allow derivatization during ionization. The accelerated reaction rates seen in charged microdroplets are useful in small-scale rapid chemical synthesis.

  14. 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

  15. Martian Atmospheric Pressure Static Charge Elimination Tool

    NASA Technical Reports Server (NTRS)

    Johansen, Michael R.

    2014-01-01

    A Martian pressure static charge elimination tool is currently in development in the Electrostatics and Surface Physics Laboratory (ESPL) at NASA's Kennedy Space Center. In standard Earth atmosphere conditions, static charge can be neutralized from an insulating surface using air ionizers. These air ionizers generate ions through corona breakdown. The Martian atmosphere is 7 Torr of mostly carbon dioxide, which makes it inherently difficult to use similar methods as those used for standard atmosphere static elimination tools. An initial prototype has been developed to show feasibility of static charge elimination at low pressure, using corona discharge. A needle point and thin wire loop are used as the corona generating electrodes. A photo of the test apparatus is shown below. Positive and negative high voltage pulses are sent to the needle point. This creates positive and negative ions that can be used for static charge neutralization. In a preliminary test, a floating metal plate was charged to approximately 600 volts under Martian atmospheric conditions. The static elimination tool was enabled and the voltage on the metal plate dropped rapidly to -100 volts. This test data is displayed below. Optimization is necessary to improve the electrostatic balance of the static elimination tool.

  16. Analysis of Sterilization Effect of Atmospheric Pressure Pulsed Plasma

    SciTech Connect

    Ekem, N.; Akan, T.; Pat, S.; Akgun, Y.; Kiremitci, A.; Musa, G.

    2007-04-23

    We have developed a new technology, the High Voltage Atmospheric Pressure Pulsed Plasma (HVAPPP), for bacteria killing. The aim of this paper is to present a simple device to generate plasma able to kill efficiently bacteria.

  17. Time-resolved characterization of a filamentary argon discharge at atmospheric pressure in a capillary using emission and absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Schröter, Sandra; Pothiraja, Ramasamy; Awakowicz, Peter; Bibinov, Nikita; Böke, Marc; Niermann, Benedikt; Winter, Jörg

    2013-11-01

    An argon/nitrogen (0.999/0.001) filamentary pulsed discharge operated at atmospheric pressure in a quartz tube is characterized using voltage-current measurements, microphotography, optical emission spectroscopy (OES) and absorption spectroscopy. Nitrogen is applied as a sensor gas for the purpose of OES diagnostic. The density of argon metastable atoms Ar(3P2) is determined using tunable diode laser absorption spectroscopy (TDLAS). Using a plasma chemical model the measured OES data are applied for the characterization of the plasma conditions. Between intense positive pulses the discharge current oscillates with a damped amplitude. It is established that an electric current flows in this discharge not only through a thin plasma filament that is observed in the discharge image but also through the whole cross section of the quartz tube. A diffuse plasma fills the quartz tube during a time between intense current pulses. Ionization waves are propagating in this plasma between the spike and the grounded area of the tube producing thin plasma channels. The diameter of these channels increases during the pause between the propagation of ionization waves probably because of thermal expansion and diffusion. Inside the channels electron densities of ˜2 × 1013 cm-3, argon metastable densities ˜1014 cm-3 and a reduced electric field about 10 Td are determined.

  18. Design and performance of an atmospheric pressure sampling interface for ion-trap/time-of-flight mass spectrometry

    SciTech Connect

    Setz, Patrick D.; Schmitz, Thomas A.; Zenobi, Renato

    2006-02-15

    An ion-trap/time-of-flight mass spectrometer in combination with an atmospheric pressure sampling interface was developed in order to simultaneously profit from the ease of sample handling at ambient pressure, from the storage and accumulation capabilities of an ion trap, and from the acquisition speed and sensitivity of a time-of-flight mass spectrometer. The sampling interface is an intermediate-pressure vacuum manifold that serves to enrich sampled analytes by jet separation with respect to the carrier gas (air) and simultaneously maintain vacuum conditions inside the ion-trap/time-of-flight instrument. Neutral analyte molecules are sampled and later ionized either by electron impact or chemical ionization. Ion accumulation is performed with a rf-only quadrupole ion trap with ground potential on the end caps during storage. For mass analysis, the trap's electrodes serve as a pulsed ion source for the attached linear time-of-flight mass spectrometer. In addition, laser desorbed molecules can also be sampled with this kind of instrument. Successful operation is shown by analyzing volatile substances (aniline, bromobenzene, styrene, and perfluorotributylamine), as well as laser-desorbed organic solids. Figures of merit include a sensitivity of 10 ppm, resolving power of 300 and demonstration of a mass spectrum of laser-desorbed anthracene with a signal-to-noise ratio of 270.

  19. Quantification of hydroxyacetone and glycolaldehyde using chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    St. Clair, J. M.; Spencer, K. M.; Beaver, M. R.; Crounse, J. D.; Paulot, F.; Wennberg, P. O.

    2014-04-01

    Chemical ionization mass spectrometry (CIMS) enables online, rapid, in situ detection and quantification of hydroxyacetone and glycolaldehyde. Two different CIMS approaches are demonstrated employing the strengths of single quadrupole mass spectrometry and triple quadrupole (tandem) mass spectrometry. Both methods are generally capable of the measurement of hydroxyacetone, an analyte with known but minimal isobaric interferences. Tandem mass spectrometry provides direct separation of the isobaric compounds glycolaldehyde and acetic acid using distinct, collision-induced dissociation daughter ions. The single quadrupole CIMS measurement of glycolaldehyde was demonstrated during the ARCTAS-CARB (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites - California Air Resources Board) 2008 campaign, while triple quadrupole CIMS measurements of glycolaldehyde and hydroxyacetone were demonstrated during the BEARPEX (Biosphere Effects on Aerosols and Photochemistry Experiment) 2009 campaign. Enhancement ratios of glycolaldehyde in ambient biomass-burning plumes are reported for the ARCTAS-CARB campaign. BEARPEX observations are compared to simple photochemical box model predictions of biogenic volatile organic compound oxidation at the site.

  20. Assessment of Atmospheric Pressure Plasma Treatment for Implant Osseointegration

    PubMed Central

    Danna, Natalie R.; Beutel, Bryan G.; Tovar, Nick; Witek, Lukasz; Marin, Charles; Granato, Rodrigo; Suzuki, Marcelo; Coelho, Paulo G.

    2015-01-01

    This study assessed the osseointegrative effects of atmospheric pressure plasma (APP) surface treatment for implants in a canine model. Control surfaces were untreated textured titanium (Ti) and calcium phosphate (CaP). Experimental surfaces were their 80-second air-based APP-treated counterparts. Physicochemical characterization was performed to assess topography, surface energy, and chemical composition. One implant from each control and experimental group (four in total) was placed in one radius of each of the seven male beagles for three weeks, and one implant from each group was placed in the contralateral radius for six weeks. After sacrifice, bone-to-implant contact (BIC) and bone area fraction occupancy (BAFO) were assessed. X-ray photoelectron spectroscopy showed decreased surface levels of carbon and increased Ti and oxygen, and calcium and oxygen, posttreatment for Ti and CaP surfaces, respectively. There was a significant (P < 0.001) increase in BIC for APP-treated textured Ti surfaces at six weeks but not at three weeks or for CaP surfaces. There were no significant (P = 0.57) differences for BAFO between treated and untreated surfaces for either material at either time point. This suggests that air-based APP surface treatment may improve osseointegration of textured Ti surfaces but not CaP surfaces. Studies optimizing APP parameters and applications are warranted. PMID:26090443

  1. Non-Thermal Atmospheric-Pressure Plasma Possible Application in Wound Healing

    PubMed Central

    Haertel, Beate; von Woedtke, Thomas; Weltmann, Klaus-Dieter; Lindequist, Ulrike

    2014-01-01

    Non-thermal atmospheric-pressure plasma, also named cold plasma, is defined as a partly ionized gas. Therefore, it cannot be equated with plasma from blood; it is not biological in nature. Non-thermal atmospheric-pressure plasma is a new innovative approach in medicine not only for the treatment of wounds, but with a wide-range of other applications, as e.g. topical treatment of other skin diseases with microbial involvement or treatment of cancer diseases. This review emphasizes plasma effects on wound healing. Non-thermal atmospheric-pressure plasma can support wound healing by its antiseptic effects, by stimulation of proliferation and migration of wound relating skin cells, by activation or inhibition of integrin receptors on the cell surface or by its pro-angiogenic effect. We summarize the effects of plasma on eukaryotic cells, especially on keratinocytes in terms of viability, proliferation, DNA, adhesion molecules and angiogenesis together with the role of reactive oxygen species and other components of plasma. The outcome of first clinical trials regarding wound healing is pointed out. PMID:25489414

  2. Particle-in-Cell Simulations of Atmospheric Pressure He/2%H2O Discharges

    NASA Astrophysics Data System (ADS)

    Kawamura, E.; Lieberman, M. A.; Lichtenberg, A. J.; Graves, D. B.; Gopalakrishnan, R.

    2015-09-01

    Atmospheric pressure micro-discharges in contact with liquid surfaces are of increasing interest, especially in the bio-medical field. We conduct 1D3v particle-in-cell (PIC) simulations of a voltage-driven 1 mm width atmospheric pressure He/2% H2O plasma discharge in series with an 0.5 mm width liquid H2O layer and a 1mm width quartz dielectric layer. A previously developed two-temperature hybrid global model of atmospheric pressure He/H2O discharges was used to determine the most important species and collisional reactions to use in the PIC simulations. We found that H13O6+, H5O3-, and electrons were the most prominent charged species, while most of the metastable helium He* was quenched via Penning ionization. The ion-induced secondary emission coefficient γi was assumed to be 0.15 at all surfaces. A series of simulations were conducted at 27.12 MHz with Jrf ~ 800-2200 A/m2. The H2O rotational and vibrational excitation losses were so high that electrons reached the walls at thermal temperatures. We also simulated a much lower frequency case of 50 kHz with Vrf = 10 kV. In this case, the discharge ran in a pure time-varying γ-mode. This work was supported by the Department of Energy Office of Fusion Energy Science Contract DE-SC0001939.

  3. EDITORIAL: Atmospheric pressure non-thermal plasmas for processing and other applications

    NASA Astrophysics Data System (ADS)

    Massines, Françoise

    2005-02-01

    Interest has grown over the past few years in applying atmospheric pressure plasmas to plasma processing for the benefits this can offer to existing and potential new processes, because they do not require expensive vacuum systems and batch processing. There have been considerable efforts to efficiently generate large volumes of homogeneous atmospheric pressure non-thermal plasmas to develop environmentally friendly alternatives for surface treatment, thin film coating, sterilization, decontamination, etc. Many interesting questions have arisen that are related to both fundamental and applied research in this field. Many concern the generation of a large volume discharge which remains stable and uniform at atmospheric pressure. At this pressure, depending on the experimental conditions, either streamer or Townsend breakdown may occur. They respectively lead to micro-discharges or to one large radius discharge, Townsend or glow. However, the complexity arises from the formation of large radius streamers due to avalanche coupling and from the constriction of the glow discharge due to too low a current. Another difficulty is to visually distinguish many micro-discharges from one large radius discharge. Other questions relate to key chemical reactions in the plasma and at the surface. Experimental characterization and modelling also need to be developed to answer these questions. This cluster collects up-to-date research results related to the understanding of different discharges working at atmospheric pressure and the application to polymer surface activation and thin film coating. It presents different solutions for generating and sustaining diffuse discharges at atmospheric pressure. DC, low-frequency and radio-frequency excitations are considered in noble gases, nitrogen or air. Two specific methods developed to understand the transition from Townsend to streamer breakdown are also presented. They are based on the cross-correlation spectroscopy and an electrical

  4. Atmospheric-Pressure Cold Plasma Induces Transcriptional Changes in Ex Vivo Human Corneas

    PubMed Central

    Rosani, Umberto; Tarricone, Elena; Venier, Paola; Brun, Paola; Deligianni, Velika; Zuin, Matteo; Martines, Emilio

    2015-01-01

    Background Atmospheric pressure cold plasma (APCP) might be considered a novel tool for tissue disinfection in medicine since the active chemical species produced by low plasma doses, generated by ionizing helium gas in air, induces reactive oxygen species (ROS) that kill microorganisms without substantially affecting human cells. Objectives In this study, we evaluated morphological and functional changes in human corneas exposed for 2 minutes (min) to APCP and tested if the antioxidant n-acetyl l-cysteine (NAC) was able to inhibit or prevent damage and cell death. Results Immunohistochemistry and western blotting analyses of corneal tissues collected at 6 hours (h) post-APCP treatment demonstrated no morphological tissue changes, but a transient increased expression of OGG1 glycosylase that returned to control levels in 24 h. Transcriptome sequencing and quantitative real time PCR performed on different corneas revealed in the treated corneas many differentially expressed genes: namely, 256 and 304 genes showing expression changes greater than ± 2 folds in the absence and presence of NAC, respectively. At 6 h post-treatment, the most over-expressed gene categories suggested an active or enhanced cell functioning, with only a minority of genes specifically concerning oxidative DNA damage and repair showing slight over-expression values (<2 folds). Moreover, time-related expression analysis of eight genes up-regulated in the APCP-treated corneas overall demonstrated the return to control expression levels after 24 h. Conclusions These findings of transient oxidative stress accompanied by wide-range transcriptome adjustments support the further development of APCP as an ocular disinfectant. PMID:26203910

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  6. Processing materials inside an atmospheric-pressure radiofrequency nonthermal plasma discharge

    DOEpatents

    Selwyn, Gary S.; Henins, Ivars; Park, Jaeyoung; Herrmann, Hans W.

    2006-04-11

    Apparatus for the processing of materials involving placing a material either placed between an radio-frequency electrode and a ground electrode, or which is itself one of the electrodes. This is done in atmospheric pressure conditions. The apparatus effectively etches or cleans substrates, such as silicon wafers, or provides cleaning of spools and drums, and uses a gas containing an inert gas and a chemically reactive gas.

  7. Dynamics of a wire-to-cylinder atmospheric pressure high-voltage nanosecond discharge

    SciTech Connect

    Levko, Dmitry; Raja, Laxminarayan L.

    2015-08-15

    The dynamics of a wire-to-cylinder atmospheric pressure high-voltage nanosecond discharge is studied by the one-dimensional Particle-in-Cell Monte Carlo collisions model in cylindrical coordinates. The x-ray photons emitted from the anode are found to be inconsequential to the generation of dense plasma in the gap. Rather, the electron impact ionization resulting from acceleration of naturally occurring background electrons in the discharge gap are enough to explain the generation of high-density (∼10{sup 15 }cm{sup −3}) non-equilibrium plasma. The influence of the high-voltage rise time on the plasma parameters is discussed.

  8. Prediction of atmospheric pressure glow discharge in dielectric-barrier system

    NASA Astrophysics Data System (ADS)

    Duan, Xiaoxi; He, Feng; Ouyang, Jiting

    2010-06-01

    A one-dimensional fluid model was used to investigate the breakdown mechanism and discharge mode in dielectric-barrier system. The results show that the dielectric barrier discharge mode depends strongly on the gas property (i.e., the electron multiplication). The atmospheric pressure dielectric barrier glow discharge could only be achieved in a gas (e.g., noble gas) in which the first Townsend ionization coefficient is sufficiently small and the electron multiplication does not rise up rapidly with the electric field, while could not be sustained in the gas (e.g., N2 and O2) in which the electron multiplication is sensitive to the field.

  9. Free-floating atmospheric pressure ball plasmas

    NASA Astrophysics Data System (ADS)

    Wurden, G. A.; Ticos, C.; Wang, Z.; Wurden, C. J. V.

    2007-11-01

    A long-lived (0.3 second, 10-20 cm diameter) ball plasma floating in the air above a water surface has been formed and studied in the laboratory. A 0.4 - 1 mF capacitor is charged to 4-5 kV, and subsequently discharged (30-60 Amps, 20-50 msec duration) into central copper cathode held fixed just below the surface of a bucket of water (with a weak solution of various salts in distilled water, such as CuSO4 or CuCl2, LiCl or NaCl). An underwater ring anode completes the circuit. A bubble of hot vapor from the water surface rises up in the first few milliseconds, and changes from a mushroom cloud with stalk, to a detached quasi-spherical object, finally evolving into a vortex ring. The plasma consists of ionized water vapor, with positive salts and OH- radicals, as well as molecular species, and it completely excludes nitrogen or oxygen from the rising plasma structure. A fine boundary layer is visible in orange, in contrast to a green ball interior when using Cu/CuSO4, and filamentary structures are visible at late times. Finally, a whisp of smoke ring is observed as a residue. A variety of visible and infrared imaging (both video and still cameras) are used, along with 200-800 nm time & space resolved spectroscopy, to identify features of this laboratory analog to ball lightning. Possible applications include a windowless ball- plasma powered pulsed copper vapor laser operating at 510 nm.

  10. Atmospheric pressure microwave assisted heterogeneous catalytic reactions.

    PubMed

    Chemat-Djenni, Zoubida; Hamada, Boudjema; Chemat, Farid

    2007-01-01

    The purpose of the study was to investigate microwave selective heating phenomena and their impact on heterogeneous chemical reactions. We also present a tool which will help microwave chemists to answer to such questions as "My reaction yields 90% after 7 days at reflux; is it possible to obtain the same yield after a few minutes under microwaves?" and to have an approximation of their reactions when conducted under microwaves with different heterogeneous procedures. This model predicting reaction kinetics and yields under microwave heating is based on the Arrhenius equation, in agreement with experimental data and procedures. PMID:17909495

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

    EPA Science Inventory

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

  12. Atmospheric pressure chemical vapour deposition of vanadium oxides

    NASA Astrophysics Data System (ADS)

    Manning, Troy Darrell

    The APCVD of vanadium(IV) oxide thin films from halide precursors was investigated. It was found that the phase of vanadium oxide obtained could be controlled by the reactor temperature and precursor ratio. For vanadium(IV) chloride and water, reactor temperatures > 550 °C and an excess of water over VCI4 was required to produce VO2 thin films. For vanadium(V) oxytrichloride and water, reactor temperatures > 550 °C and an excess of water over VOCI3 also produced VO2 but required low total gas flow rates (< 1 L min 1) for complete coverage of the substrate. Vanadium(IV) oxide thin films doped with metal ions (W, Cr, Nb, Ti, Mo or Sn) were also prepared by the APCVD process in order to reduce the thermochromic transition temperature (TC) from 68 °C for the undoped material to < 30 °C. The most successful dopant was tungsten, introduced into the VOCl3, and water system as WCI6, which lowered T to 5 °C for a 3 atom% tungsten doped thin film. Tungsten (VI) ethoxide was introduced into the VCI4 and water system and reduced TC, of VO2, to 42 °C for a 1 atom% tungsten doped thin film. Chromium, introduced as CrCO2Cl2, formed a chromium vanadium oxide that did not display any thermochromic properties. Niobium, introduced as NbCl5 into the VOCl3 system, reduced TC of VO2, but the amount of niobium introduced could not be easily controlled. Molybdenum, introduced as MoCI5, also reduced TC of VO2, but the form of the molybdenum appeared to be different from that required for complete control of TC, Titanium, introduced as TiCl4, produced phase segregated films of VO2 and TiO2, with interesting multifunctional properties and a reduced TC. Tin, introduced as SnCl4, also formed a phase segregated material of VO2, and SnO2, with a slightly reduced TC.

  13. Free radicals induced in aqueous solution by non-contact atmospheric-pressure cold plasma

    SciTech Connect

    Tani, Atsushi; Fukui, Satoshi; Ono, Yusuke; Kitano, Katsuhisa; Ikawa, Satoshi

    2012-06-18

    To understand plasma-induced chemical processing in liquids, we investigated the formation of free radicals in aqueous solution exposed to different types of non-contact atmospheric-pressure helium plasma using the spin-trapping technique. Both hydroxyl radical (OH{center_dot}) and superoxide anion radical (O{sub 2}{sup -}{center_dot}) adducts were observed when neutral oxygen gas was additionally supplied to the plasma. In particular, O{sub 2}{sup -}{center_dot} can be dominantly induced in the solution via oxygen flow into the afterglow gas of helium plasma. This type of plasma treatment can potentially be used in medical applications to control infectious diseases, because the O{sub 2}{sup -}{center_dot} is crucial for sterilization of liquids via atmospheric-pressure plasma.

  14. Tailoring non-equilibrium atmospheric pressure plasmas for healthcare technologies

    NASA Astrophysics Data System (ADS)

    Gans, Timo

    2012-10-01

    Non-equilibrium plasmas operated at ambient atmospheric pressure are very efficient sources for energy transport through reactive neutral particles (radicals and metastables), charged particles (ions and electrons), UV radiation, and electro-magnetic fields. This includes the unique opportunity to deliver short-lived highly reactive species such as atomic oxygen and atomic nitrogen. Reactive oxygen and nitrogen species can initiate a wide range of reactions in biochemical systems, both therapeutic and toxic. The toxicological implications are not clear, e.g. potential risks through DNA damage. It is anticipated that interactions with biological systems will be governed through synergies between two or more species. Suitable optimized plasma sources are improbable through empirical investigations. Quantifying the power dissipation and energy transport mechanisms through the different interfaces from the plasma regime to ambient air, towards the liquid interface and associated impact on the biological system through a new regime of liquid chemistry initiated by the synergy of delivering multiple energy carrying species, is crucial. The major challenge to overcome the obstacles of quantifying energy transport and controlling power dissipation has been the severe lack of suitable plasma sources and diagnostic techniques. Diagnostics and simulations of this plasma regime are very challenging; the highly pronounced collision dominated plasma dynamics at very small dimensions requires extraordinary high resolution - simultaneously in space (microns) and time (picoseconds). Numerical simulations are equally challenging due to the inherent multi-scale character with very rapid electron collisions on the one extreme and the transport of chemically stable species characterizing completely different domains. This presentation will discuss our recent progress actively combining both advance optical diagnostics and multi-scale computer simulations.

  15. Collaborative Research. Atmospheric Pressure Microplasma Chemistry-Photon Synergies

    SciTech Connect

    Park, Sung-Jin; Eden, James Gary

    2015-12-01

    Combining the effects of low temperature, atmospheric pressure microplasmas and microplasma photon sources offers the promise of greatly expanding the range of applications for each of them. The plasma sources create active chemical species and these can be activated further by the addition of photons and the associated photochemistry. There are many ways to combine the effects of plasma chemistry and photochemistry, especially if there are multiple phases present. This project combined the construction of appropriate test experimental systems, various spectroscopic diagnostics and mathematical modeling. Through a continuous discussion and co-design process with the UC-Berkeley Team, we have successfully completed the fabrication and testing of all components for a microplasma array-assisted system designed for photon-activated plasma chemistry research. Microcavity plasma lamps capable of generating more than 20 mW/cm2 at 172 nm (Xe dimer) were fabricated with a custom form factor to mate to the plasma chemistry setup, and a lamp was current being installed by the Berkeley team so as to investigate plasma chemistry-photon synergies at a higher photon energy (~7.2 eV) as compared to the UVA treatment that is afforded by UV LEDs operating at 365 nm. In particular, motivated by the promising results from the Berkeley team with UVA treatment, we also produced the first generation of lamps that can generate photons in the 300-370 nm wavelength range. Another set of experiments, conducted under the auspices of this grant, involved the use of plasma microjet arrays. The combination of the photons and excited radicals produced by the plasma column resulted in broad area deactivation of bacteria.

  16. A simplified nitrogen laser setup operated at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Ruangsri, Artit; Wungmool, Piyachat; Tesana, Siripong; Suwanatus, Suchat; Hormwantha, Tongchai; Chiangga, Surasak; Luengviriya, Chaiya

    2015-07-01

    A transversely excited atmospheric pressure nitrogen laser (TEA N2 Laser) is a molecular pulse gas laser, operated at atmospheric pressure, which generates an electromagnetic wave in ultraviolet wavelength of 337.1 nm. It can operate without an optical resonator. We present a TEA N2 laser setup excited by an electronic discharge circuit known as the Blumlein circuit. Our setup is composed of simple components commonly found in everyday life. The setup can be utilized in classroom to demonstrate the dependence of the laser intensity on the flow rate of nitrogen gas.

  17. Statistical analysis of ionosphere parameters and atmospheric pressure correlations

    NASA Astrophysics Data System (ADS)

    Voloskov, Dmitriy; Bochkarev, Vladimir; Maslennikova, Yulia; Zagidullin, Bulat

    Ionosphere parameters such as Total electron content (TEC) and Doppler frequency shift characterize ionosphere influence on signals propagation, and therefore information about these parameters is important for radio communication tasks. Meteorological effects such as atmospheric pressure variations can influence on ionosphere parameters. This work is dedicated to analysis of correlations between meteorological and ionosphere parameters. NCEP/NCAR reanalysis meteorological maps, Jet Propulsion Laboratory (JPL) global TEC maps and data from Doppler phase goniometric complex “Spectr” were analysed. Data for 2009-2011 were investigated. Coherent oscillations with periods of 29-32 and 4 days were detected in atmospheric pressure and Doppler frequency shift variations.

  18. Atmospheric pressure plasma polymerization of 1,3-butadiene for hydrophobic finishing of textile substrates

    NASA Astrophysics Data System (ADS)

    Samanta, Kartick K.; Jassal, Manjeet; Agrawal, Ashwini K.

    2010-02-01

    Atmospheric pressure plasma processing of textile has both ecological and economical advantages over the wet-chemical processing. However, reaction in atmospheric pressure plasma has important challenges to be overcome before it can be successfully used for finishing applications in textile. These challenges are (i) generating stable glow plasma in presence liquid/gaseous monomer, and (ii) keeping the generated radicals active in the presence of contaminants such as oxygen and air. In this study, a stable glow plasma was generated at atmospheric pressure in the mixture of gaseous reactive monomer-1,3-butadiene and He and was made to react with cellulosic textile substrate. After 12 min of plasma treatment, the hydrophilic surface of the cellulosic substrate turned into highly hydrophobic surface. The hydrophobic finish was found to be durable to soap washing. After soap washing, a water drop of 37 μl took around 250 s to get absorbed in the treated sample compared to < 1 s in the untreated samples. The plasma modified samples showed water contact angle of around 134°. Both top and bottom sides of the fabric showed similar hydrophobic results in terms of water absorbency and contact angle. The results may be attributed to chemical reaction of butadiene with the cellulosic textile substrate. The surface characterization of the plasma modified samples under SEM and AFM revealed modification of the surface under <100 nm. The results showed that atmospheric pressure plasma can be successfully used for carrying out reaction of 1,3-butadiene with cellulosic textile substrates for producing hydrophobic surface finish.

  19. Chemical-ionization visible and ultraviolet gas lasers: A concept

    NASA Technical Reports Server (NTRS)

    Laudenslager, J. B.

    1975-01-01

    Charge-transfer reactions or Penning ionization reactions are used to produce population inversions between electronic states of molecular ions which should result in stimulated emission in ultraviolet and visible regions. Such lasers could be used in study of short-lived reaction intermediates, crystal structure and scattering, and photolysis.

  20. Atmospheric pressure photoionization as a powerful tool for large-scale lipidomic studies.

    PubMed

    Gaudin, Mathieu; Imbert, Laurent; Libong, Danielle; Chaminade, Pierre; Brunelle, Alain; Touboul, David; Laprévote, Olivier

    2012-05-01

    Lipidomic studies often use liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) for separation, identification, and quantification. However, due to the wide structural diversity of lipids, the most apolar part of the lipidome is often detected with low sensitivity in ESI. Atmospheric pressure (APPI) can be an alternative ionization source since normal-phase solvents are known to enhance photoionization of these classes. In this paper, we intend to show the efficiency of APPI to identify different lipid classes, with a special interest on sphingolipids. In-source APPI fragmentation appears to be an added value for the structural analysis of lipids. It provides a detailed characterization of both the polar head and the non polar moiety of most lipid classes, and it makes possible the detection of all lipids in both polarities, which is not always possible with ESI. PMID:22359092

  1. Atmospheric pressure helium afterglow discharge detector for gas chromatography

    DOEpatents

    Rice, Gary; D'Silva, Arthur P.; Fassel, Velmer A.

    1986-05-06

    An apparatus for providing a simple, low-frequency electrodeless discharge system for atmospheric pressure afterglow generation. A single quartz tube through which a gas mixture is passed is extended beyond a concentric electrode positioned thereabout. A grounding rod is placed directly above the tube outlet to permit optical viewing of the discharge between the electrodes.

  2. Atmospheric pressure helium afterglow discharge detector for gas chromatography

    DOEpatents

    Rice, G.; D'Silva, A.P.; Fassel, V.A.

    1985-04-05

    An apparatus for providing a simple, low-frequency, electrodeless discharge system for atmospheric pressure afterglow generation. A single quartz tube through which a gas mixture is passed is extended beyond a concentric electrode positioned thereabout. A grounding rod is placed directly above the tube outlet to permit optical viewing of the discharge between the electrodes.

  3. ANNUAL REPORT. ATMOSPHERIC-PRESSURE PLASMA CLEANING OF CONTAMINATED SURFACES

    EPA Science Inventory

    The objective of this work is to demonstrate a practical, atmospheric pressure plasma tool for the surface decontamination of nuclear waste. Decontamination of radioactive materials that have accumulated on the surfaces of equipment and structures is a challenging and costly unde...

  4. Carbonation of epoxy methyl soyate at atmospheric pressure

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Carbonated methyl soyates were prepared from epoxy methyl soyate by the introduction of carbon dioxide at the oxirane position. Carbonation was performed with carbon dioxide gas by sparging carbon dioxide through the epoxy esters at atmospheric pressure in the presence of tetrabutylammonium bromide...

  5. Electrolytic synthesis of ammonia in molten salts under atmospheric pressure.

    PubMed

    Murakami, Tsuyoshi; Nishikiori, Tokujiro; Nohira, Toshiyuki; Ito, Yasuhiko

    2003-01-15

    Ammonia was successfully synthesized by using a new electrochemical reaction with high current efficiency at atmospheric pressure and at lower temperatures than the Haber-Bosch process. In this method, nitride ion (N3-), which is produced by the reduction from nitrogen gas at the cathode, is anodically oxidized and reacts with hydrogen to produce ammonia at the anode. PMID:12517136

  6. Application of Relationship Between Groundwater Level and Atmospheric Pressure Change

    NASA Astrophysics Data System (ADS)

    Kim, S. J.; Lee, K.

    2013-12-01

    Change in atmospheric pressure affects ground water levels. Barometric efficiency, which is an indicator for different exposure to the atmospheric pressure of observation well and adjacent ground cover, can be used as an effective tool for estimating some groundwater properties. If the top of an observation well is sealed and contact with the atmosphere is blocked, there would be no pressure difference between the well and adjacent ground cover. As a result, the difference between barometric efficiency values of sealed and unsealed well of identical condition can indicates the effect of atmospheric pressure changes on the groundwater level. One month observation data of hydraulic head and atmospheric pressure at Wonju-si in Gangwon-do, Korea are used. Two different methods, Clark's method and graphical method, are adopted to estimate the barometric efficiency. Because the efficiency has implication on the properties of aquifer covering condition, mapping of this efficiency might be used for estimating groundwater vulnerability of contamination from surface-loaded sources.

  7. The effect of atmospheric pressure on ventricular assist device output.

    PubMed

    Goto, Takeshi; Sato, Masaharu; Yamazaki, Akio; Fukuda, Wakako; Watanabe, Ken-Ichi; Daitoku, Kazuyuki; Minakawa, Masahito; Fukui, Kozo; Suzuki, Yasuyuki; Fukuda, Ikuo

    2012-03-01

    The effect of cabin pressure change on the respiratory system during flight is well documented in the literature, but how the change in atmospheric pressure affects ventricular assist device (VAD) output flow has not been studied yet. The purpose of our study was to evaluate the change in VAD output using a mock circulatory system in a low-pressure chamber mimicking high altitude. Changes in output and driving pressure were measured during decompression from 1.0 to 0.7 atm and pressurization from 0.7 to 1.0 atm. Two driving systems were evaluated: the VCT system and the Mobart system. In the VCT system, output and driving pressure remained the same during decompression and pressurization. In the Mobart system, the output decreased as the atmospheric pressure dropped and recovered during pressurization. The lowest output was observed at 0.7 atm, which was 80% of the baseline driven by the Mobart system. Under a practical cabin pressure of 0.8 atm, the output driven by the Mobart system was 90% of the baseline. In the Mobart system, the output decreased as the atmospheric pressure dropped, and recovered during pressurization. However, the decrease in output was slight. In an environment where the atmospheric pressure changes, it is necessary to monitor the diaphragmatic motion of the blood pump and the driving air pressure, and to adjust the systolic:diastolic ratio as well as the positive and negative pressures in a VAD system. PMID:21915797

  8. Atmospheric pressure and suicide attempts in Helsinki, Finland

    NASA Astrophysics Data System (ADS)

    Hiltunen, Laura; Ruuhela, Reija; Ostamo, Aini; Lönnqvist, Jouko; Suominen, Kirsi; Partonen, Timo

    2012-11-01

    The influence of weather on mood and mental health is commonly debated. Furthermore, studies concerning weather and suicidal behavior have given inconsistent results. Our aim was to see if daily weather changes associate with the number of suicide attempts in Finland. All suicide attempts treated in the hospitals in Helsinki, Finland, during two separate periods, 8 years apart, were included. Altogether, 3,945 suicide attempts were compared with daily weather parameters and analyzed with a Poisson regression. We found that daily atmospheric pressure correlated statistically significantly with the number of suicide attempts, and for men the correlation was negative. Taking into account the seasonal normal value during the period 1971-2000, daily temperature, global solar radiation and precipitation did not associate with the number of suicide attempts on a statistically significant level in our study. We concluded that daily atmospheric pressure may have an impact on suicidal behavior, especially on suicide attempts of men by violent methods ( P < 0.001), and may explain the clustering of suicide attempts. Men seem to be more vulnerable to attempt suicide under low atmospheric pressure and women under high atmospheric pressure. We show only statistical correlations, which leaves the exact mechanisms of interaction between weather and suicidal behavior open. However, suicidal behavior should be assessed from the point of view of weather in addition to psychiatric and social aspects.

  9. Preparation of nanodiamonds from carbon nanoparticles at atmospheric pressure.

    PubMed

    Kamali, Ali Reza; Fray, Derek J

    2015-04-01

    A route for producing diamond nanocrystals is reported in this paper. Li2CO3 containing carbon nanostructures synthesised in molten LiCl were transformed to nanodiamonds by simple heating at atmospheric pressure, far less severe conditions than conventional processes. The method presented offers the possibility of bulk production. PMID:25650151

  10. Direct Analysis of Single Cells by Mass Spectrometry at Atmospheric Pressure

    PubMed Central

    Shrestha, Bindesh; Vertes, Akos

    2010-01-01

    Analysis of biochemicals in single cells is important for understanding cell metabolism, cell cycle, adaptation, disease states, etc. Even the same cell types exhibit heterogeneous biochemical makeup depending on their physiological conditions and interactions with the environment. Conventional methods of mass spectrometry (MS) used for the analysis of biomolecules in single cells rely on extensive sample preparation. Removing the cells from their natural environment and extensive sample processing could lead to changes in the cellular composition. Ambient ionization methods enable the analysis of samples in their native environment and without extensive sample preparation.1 The techniques based on the mid infrared (mid-IR) laser ablation of biological materials at 2.94 μm wavelength utilize the sudden excitation of water that results in phase explosion.2 Ambient ionization techniques based on mid-IR laser radiation, such as laser ablation electrospray ionization (LAESI) and atmospheric pressure infrared matrix-assisted laser desorption ionization (AP IR-MALDI), have successfully demonstrated the ability to directly analyze water-rich tissues and biofluids at atmospheric pressure.3-11 In LAESI the mid-IR laser ablation plume that mostly consists of neutral particulate matter from the sample coalesces with highly charged electrospray droplets to produce ions. Recently, mid-IR ablation of single cells was performed by delivering the mid-IR radiation through an etched fiber. The plume generated from this ablation was postionized by an electrospray enabling the analysis of diverse metabolites in single cells by LAESI-MS.12 This article describes the detailed protocol for single cell analysis using LAESI-MS. The presented video demonstrates the analysis of a single epidermal cell from the skin of an Allium cepa bulb. The schematic of the system is shown in Figure 1. A representative example of single cell ablation and a LAESI mass spectrum from the cell are provided in

  11. EDITORIAL Metal vapour in atmospheric-pressure arcs Metal vapour in atmospheric-pressure arcs

    NASA Astrophysics Data System (ADS)

    Murphy, Anthony B.

    2010-11-01

    Metal vapour has a significant, and in some cases dominant, influence in many applications of atmospheric-pressure plasmas, including arc welding, circuit interruption and mineral processing. While the influence of metal vapour has long been recognized, it is only recently that diagnostic and computational tools have been sufficiently well-developed to allow this influence to be more thoroughly examined and understood. Some unexpected findings have resulted: for example, that the presence of metal vapour in gas-metal arc welding leads to local minima in the temperature and current density in the centre of the arc. It has become clear that the presence of metal vapour, as well as having intrinsic scientific interest, plays an important role in determining the values of critical parameters in industrial applications, such as the weld penetration in arc welding and the extinction time in circuit breakers. In gas-tungsten arc welding, metal vapour concentrations are formed by evaporation of the weld pool, and are relatively low, typically at most a few per cent. Moreover, the convective flow of the plasma near the weld pool tends to direct the metal vapour plume radially outwards. In gas-metal arc welding, in contrast, metal vapour concentrations can reach over 50%. In this case, the metal vapour is produced mainly by evaporation of the wire electrode, and the strong downwards convective flow below the electrode concentrates the metal vapour in the central region of the arc. The very different metal concentrations and distributions in the two welding processes mean that the metal vapour has markedly different influences on the arc. In gas-tungsten arc welding, the current density distribution is broadened near the weld pool by the influence of the metal vapour on the electrical conductivity of the plasma, and the arc voltage is decreased. In contrast, in gas-metal arc welding, the arc centre is cooled by increased radiative emission and the arc voltage is increased. In

  12. Surface modification of aluminum by runaway electron preionized diffuse discharges in different gases at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Erofeev, Mikhail V.; Shulepov, Mikhail A.; Tarasenko, Victor F.

    2015-12-01

    The paper presents the results of an examination of aluminum samples exposed to runaway electron preionized diffuse discharges in air, nitrogen, and argon at atmospheric pressure. The changes in the chemical composition, structure, and hardness of the aluminum surface layers caused by the action of the discharge were investigated. It has been found that the oxygen and carbon concentrations in the surface layers depend on the number of discharge pulses and on the chemical composition of the working gas. The goal of the study was to find possible uses of runaway electron preionized diffuse discharges in research and industry.

  13. Atmospheric Pressure Error of GRACE in Antarctic Ice Mass Change

    NASA Astrophysics Data System (ADS)

    Kim, B.; Eom, J.; Seo, K. W.

    2014-12-01

    As GRACE has observed time-varying gravity longer than a decade, long-term mass changes have been emerged. In particular, linear trends and accelerated patterns in Antarctica were reported and paid attention for the projection of sea level rise. The cause of accelerated ice mass loss in Antarctica is not known since its amplitude is not significantly larger than ice mass change associated with natural climate variations. In this study, we consider another uncertainty in Antarctic ice mass loss acceleration due to unmodeled atmospheric pressure field. We first compare GRACE AOD product with in-situ atmospheric pressure data from SCAR READER project. GRACE AOD (ECMWF) shows spurious jump near Transantarctic Mountains, which is due to the regular model update of ECMWF. In addition, GRACE AOD shows smaller variations than in-situ observation in coastal area. This is possibly due to the lower resolution of GRACE AOD, and thus relatively stable ocean bottom pressure associated with inverted barometric effect suppresses the variations of atmospheric pressure near coast. On the other hand, GRACE AOD closely depicts in-situ observations far from oceans. This is probably because GRACE AOD model (ECMWF) is assimilated with in-situ observations. However, the in-situ observational sites in interior of Antarctica are sparse, and thus it is still uncertain the reliability of GRACE AOD for most region of Antarctica. To examine this, we cross-validate three different reanalysis; ERA Interim, NCEP DOE and MERRA. Residual atmospheric pressure fields as a measure of atmospheric pressure errors, NCEP DOE - ERA Interim or MERRA - ERA Interim, show long-term changes, and the estimated uncertainty in acceleration of Antarctic ice mass change is about 9 Gton/yr^2 from 2003 to 2012. This result implies that the atmospheric surface pressure error likely hinders the accurate estimate of the ice mass loss acceleration in Antarctica.

  14. Small molecule ambient mass spectrometry imaging by infrared laser ablation metastable-induced chemical ionization.

    PubMed

    Galhena, Asiri S; Harris, Glenn A; Nyadong, Leonard; Murray, Kermit K; Fernández, Facundo M

    2010-03-15

    Presented here is a novel ambient ion source termed infrared laser ablation metastable-induced chemical ionization (IR-LAMICI). IR-LAMICI integrates IR laser ablation and direct analysis in real time (DART)-type metastable-induced chemical ionization for open air mass spectrometry (MS) ionization. The ion generation in the IR-LAMICI source is a two step process. First, IR laser pulses impinge the sample surface ablating surface material. Second, a portion of ablated material reacts with the metastable reactive plume facilitating gas-phase chemical ionization of analyte molecules generating protonated or deprotonated species in positive and negative ion modes, respectively. The successful coupling of IR-laser ablation with metastable-induced chemical ionization resulted in an ambient plasma-based spatially resolved small molecule imaging platform for mass spectrometry (MS). The analytical capabilities of IR-LAMICI are explored by imaging pharmaceutical tablets, screening counterfeit drugs, and probing algal tissue surfaces for natural products. The resolution of a chemical image is determined by the crater size produced with each laser pulse but not by the size of the metastable gas jet. The detection limits for an active pharmaceutical ingredient (acetaminophen) using the IR-LAMICI source is calculated to be low picograms. Furthermore, three-dimensional computational fluid dynamic simulations showed improvements in the IR-LAMICI ion source are possible. PMID:20155978

  15. Final Report - Ion Production and Transport in Atmospheric Pressure Ion Source Mass Spectrometers

    SciTech Connect

    Farnsworth, Paul B.; Spencer, Ross L.

    2014-05-14

    This document is the final report on a project that focused in the general theme of atmospheric-pressure ion production and transport for mass spectrometry. Within that general theme there were two main projects: the fundamental study of the transport of elemental ions through the vacuum interface of an inductively coupled plasma mass spectrometer (ICPMS), and fundamental studies of the ionization mechanisms in ambient desorption/ionization (ADI) sources for molecular mass spectrometry. In both cases the goal was to generate fundamental understanding of key instrumental processes that would lead to the development of instruments that were more sensitive and more consistent in their performance. The emphasis on consistency derives from the need for instruments that have the same sensitivity, regardless of sample type. In the jargon of analytical chemistry, such instruments are said to be free from matrix effects. In the ICPMS work each stage of ion production and of ion transport from the atmospheric pressure to the high-vacuum mass analyzer was studied. Factors controlling ion transport efficiency and consistency were identified at each stage of pressure reduction. In the ADI work the interactions between an electrospray plume and a fluorescent sample on a surface were examined microscopically. A new mechanism for analyte ion production in desorption electrospray ionization (DESI) was proposed. Optical spectroscopy was used to track the production of reactive species in plasmas used as ADI sources. Experiments with mixed-gas plasmas demonstrated that the addition of a small amount of hydrogen to a helium ADI plasma could boost the sensitivity for some analytes by over an order of magnitude.

  16. Atmospheric pressure plasma jet for liquid spray treatment

    NASA Astrophysics Data System (ADS)

    Mitić, S.; Philipps, J.; Hofmann, D.

    2016-05-01

    Atmospheric pressure plasma jets have been intensively studied in recent years due to growing interest in their use for biomedical applications and surface treatments. Either surfaces can be treated by a plasma jet afterglow for cleaning or activation or a material can be deposited by a reactive gas component activated by plasma. Effects of plasma on liquid have been reported several times where the electron spin trapping method was used for radical detection. Here we propose another method of liquid treatment using the atmospheric pressure plasma jet. In the device presented here, liquid was sprayed in droplets from an inner electrode directly into a plasma jet where it was treated and sprayed out by gas flow. Optical end electrical measurements were done for diagnostics of the plasma while electron paramagnetic resonance measurements were used for detection of radicals (\\text{OH},\\text{OOH},\\text{CH} ) produced by plasma treatment of liquids.

  17. Atmospheric-pressure guided streamers for liposomal membrane disruption

    NASA Astrophysics Data System (ADS)

    Svarnas, P.; Matrali, S. H.; Gazeli, K.; Aleiferis, Sp.; Clément, F.; Antimisiaris, S. G.

    2012-12-01

    The potential to use liposomes (LIPs) as a cellular model in order to study interactions of cold atmospheric-pressure plasma with cells is herein investigated. Cold atmospheric-pressure plasma is formed by a dielectric-barrier discharge reactor. Large multilamellar vesicle liposomes, consisted of phosphatidylcholine and cholesterol, are prepared by the thin film hydration technique, to encapsulate a small hydrophilic dye, i.e., calcein. The plasma-induced release of calcein from liposomes is then used as a measure of liposome membrane integrity and, consequently, interaction between the cold atmospheric plasma and lipid bilayers. Physical mechanisms leading to membrane disruption are suggested, based on the plasma characterization including gas temperature calculation.

  18. Atmospheric-pressure guided streamers for liposomal membrane disruption

    SciTech Connect

    Svarnas, P.; Aleiferis, Sp.; Matrali, S. H.; Gazeli, K.; Clement, F.; Antimisiaris, S. G.

    2012-12-24

    The potential to use liposomes (LIPs) as a cellular model in order to study interactions of cold atmospheric-pressure plasma with cells is herein investigated. Cold atmospheric-pressure plasma is formed by a dielectric-barrier discharge reactor. Large multilamellar vesicle liposomes, consisted of phosphatidylcholine and cholesterol, are prepared by the thin film hydration technique, to encapsulate a small hydrophilic dye, i.e., calcein. The plasma-induced release of calcein from liposomes is then used as a measure of liposome membrane integrity and, consequently, interaction between the cold atmospheric plasma and lipid bilayers. Physical mechanisms leading to membrane disruption are suggested, based on the plasma characterization including gas temperature calculation.

  19. Atmospheric-pressure plasma sources for biomedical applications

    NASA Astrophysics Data System (ADS)

    Park, G. Y.; Park, S. J.; Choi, M. Y.; Koo, I. G.; Byun, J. H.; Hong, J. W.; Sim, J. Y.; Collins, G. J.; Lee, J. K.

    2012-08-01

    Atmospheric-pressure plasmas (APPs) have attracted great interest and have been widely applied in biomedical applications, as due to their non-thermal and reactive properties, they interact with living tissues, cells and bacteria. Various types of plasma sources generated at atmospheric pressure have been developed to achieve better performance in specific applications. This article presents an overview of the general characteristics of APPs and a brief summary of their biomedical applications, and reviews a wide range of these sources developed for biomedical applications. The plasma sources are classified according to their power sources and cover a wide frequency spectrum from dc to microwaves. The configurations and characteristics of plasma sources are outlined and their biomedical applications are presented.

  20. Cellular membrane collapse by atmospheric-pressure plasma jet

    SciTech Connect

    Kim, Kangil; Sik Yang, Sang E-mail: ssyang@ajou.ac.kr; Jun Ahn, Hak; Lee, Jong-Soo E-mail: ssyang@ajou.ac.kr; Lee, Jae-Hyeok; Kim, Jae-Ho

    2014-01-06

    Cellular membrane dysfunction caused by air plasma in cancer cells has been studied to exploit atmospheric-pressure plasma jets for cancer therapy. Here, we report that plasma jet treatment of cervical cancer HeLa cells increased electrical conductivity across the cellular lipid membrane and caused simultaneous lipid oxidation and cellular membrane collapse. We made this finding by employing a self-manufactured microelectrode chip. Furthermore, increased roughness of the cellular lipid membrane and sequential collapse of the membrane were observed by atomic force microscopy following plasma jet treatment. These results suggest that the cellular membrane catastrophe occurs via coincident altered electrical conductivity, lipid oxidation, and membrane roughening caused by an atmospheric-pressure plasma jet, possibly resulting in cellular vulnerability to reactive species generated from the plasma as well as cytotoxicity to cancer cells.

  1. A decadal precession of atmospheric pressures over the North Pacific

    NASA Astrophysics Data System (ADS)

    Anderson, Bruce T.; Gianotti, Daniel J. S.; Furtado, Jason C.; Di Lorenzo, Emanuele

    2016-04-01

    Sustained droughts over the Northwestern U.S. can alter water availability to the region's agricultural, hydroelectric, and ecosystem service sectors. Here we analyze decadal variations in precipitation across this region and reveal their relation to the slow (~10 year) progression of an atmospheric pressure pattern around the North Pacific, which we term the Pacific Decadal Precession (PDP). Observations corroborate that leading patterns of atmospheric pressure variability over the North Pacific evolve in a manner consistent with the PDP and manifest as different phases in its evolution. Further analysis of the data indicates that low-frequency fluctuations of the tropical Pacific Ocean state energize one phase of the PDP and possibly the other through coupling with the polar stratosphere. Evidence that many recent climate variations influencing the North Pacific/North American sector over the last few years are consistent with the current phase of the PDP confirms the need to enhance our predictive understanding of its behavior.

  2. Carboxylation of Phenols with CO2 at Atmospheric Pressure.

    PubMed

    Luo, Junfei; Preciado, Sara; Xie, Pan; Larrosa, Igor

    2016-05-10

    A convenient and efficient method for the ortho-carboxylation of phenols under atmospheric CO2 pressure has been developed. This method provides an alternative to the previously reported Kolbe-Schmitt method, which requires very high pressures of CO2 . The addition of a trisubstituted phenol has proved essential for the successful carboxylation of phenols with CO2 at standard atmospheric pressure, allowing the efficient preparation of a broad variety of salicylic acids. PMID:26989848

  3. Atmospheric pressure fluctuations and oxygen enrichment in waste tanks

    SciTech Connect

    Kurzeja, R.J.; Weber, A.H.

    1993-07-01

    During In-Tank Precipitation (ITP) processing radiolytic decomposition of tetraphenylborate and water can produce benzene and hydrogen, which, given sufficiently high oxygen concentrations, can deflagrate. To prevent accumulations of benzene and hydrogen and avoid deflagration, continuous nitrogen purging is maintained. If the nitrogen purging is interrupted by, for example, a power failure, outside air will begin to seep into the tank through vent holes and cracks. Eventually a flammable mixture of benzene, hydrogen, and oxygen will occur (deflagration). However, this process is slow under steady-state conditions (constant pressure) and mechanisms to increase the exchange rate with the outside atmosphere must be considered. The most important mechanism of this kind is from atmospheric pressure fluctuations in which an increase in atmospheric pressure forces air into the tank which then mixes with the hydrogen-benzene mixture. The subsequent decrease in atmospheric pressure causes venting from the tank of the mixture -- the net effect being an increase in the tank`s oxygen concentration. Thus, enrichment occurs when the atmospheric pressure increases but not when the pressure decreases. Moreover, this natural atmospheric {open_quotes}pumping{close_quotes} is only important if the pressure fluctuations take place on a time scale longer than the characteristic mixing time scale (CMT) of the tank. If pressure fluctuations have a significantly higher frequency than the CMT, outside air will be forced into the tank and then out again before any significant mixing can occur. The CMT is not known for certain, but is estimated to be between 8 and 24 hours. The purpose of this report is to analyze yearly pressure fluctuations for a five year period to determine their statistical properties over 8 and 24-hour periods. The analysis also includes a special breakdown into summer and winter seasons and an analysis of 15-minute data from the SRTC Climatology Site.

  4. Engineering a laser remote sensor for atmospheric pressure and temperature

    NASA Technical Reports Server (NTRS)

    Kalshoven, J. E., Jr.; Korb, C. L.

    1978-01-01

    A system for the remote sensing of atmospheric pressure and temperature is described. Resonant lines in the 7600 Angstrom oxygen A band region are used and an organic dye laser beam is tuned to measure line absorption changes with temperature or pressure. A reference beam outside this band is also transmitted for calibration. Using lidar techniques, profiling of these parameters with altitude can be accomplished.

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

    SciTech Connect

    Walsh, Catherine; Millar, T. J.; Nomura, Hideko; Aikawa, Yuri

    2012-03-10

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

  6. Plant adaptation to low atmospheric pressures: potential molecular responses

    NASA Technical Reports Server (NTRS)

    Ferl, Robert J.; Schuerger, Andrew C.; Paul, Anna-Lisa; Gurley, William B.; Corey, Kenneth; Bucklin, Ray

    2002-01-01

    There is an increasing realization that it may be impossible to attain Earth normal atmospheric pressures in orbital, lunar, or Martian greenhouses, simply because the construction materials do not exist to meet the extraordinary constraints imposed by balancing high engineering requirements against high lift costs. This equation essentially dictates that NASA have in place the capability to grow plants at reduced atmospheric pressure. Yet current understanding of plant growth at low pressures is limited to just a few experiments and relatively rudimentary assessments of plant vigor and growth. The tools now exist, however, to make rapid progress toward understanding the fundamental nature of plant responses and adaptations to low pressures, and to develop strategies for mitigating detrimental effects by engineering the growth conditions or by engineering the plants themselves. The genomes of rice and the model plant Arabidopsis thaliana have recently been sequenced in their entirety, and public sector and commercial DNA chips are becoming available such that thousands of genes can be assayed at once. A fundamental understanding of plant responses and adaptation to low pressures can now be approached and translated into procedures and engineering considerations to enhance plant growth at low atmospheric pressures. In anticipation of such studies, we present here the background arguments supporting these contentions, as well as informed speculation about the kinds of molecular physiological responses that might be expected of plants in low-pressure environments.

  7. Quality characteristics of the radish grown under reduced atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Levine, Lanfang H.; Bisbee, Patricia A.; Richards, Jeffrey T.; Birmele, Michele N.; Prior, Ronald L.; Perchonok, Michele; Dixon, Mike; Yorio, Neil C.; Stutte, Gary W.; Wheeler, Raymond M.

    This study addresses whether reduced atmospheric pressure (hypobaria) affects the quality traits of radish grown under such environments. Radish (Raphanus sativus L. cv. Cherry Bomb Hybrid II) plants were grown hydroponically in specially designed hypobaric plant growth chambers at three atmospheric pressures; 33, 66, and 96 kPa (control). Oxygen and carbon dioxide partial pressures were maintained constant at 21 and 0.12 kPa, respectively. Plants were harvested at 21 days after planting, with aerial shoots and swollen hypocotyls (edible portion of the radish referred to as the “root” hereafter) separated immediately upon removal from the chambers. Samples were subsequently evaluated for their sensory characteristics (color, taste, overall appearance, and texture), taste-determining factors (glucosinolate and soluble carbohydrate content and myrosinase activity), proximate nutrients (protein, dietary fiber, and carbohydrate) and potential health benefit attributes (antioxidant capacity). In roots of control plants, concentrations of glucosinolate, total soluble sugar, and nitrate, as well as myrosinase activity and total antioxidant capacity (measured as ORACFL), were 2.9, 20, 5.1, 9.4, and 1.9 times greater than the amount in leaves, respectively. There was no significant difference in total antioxidant capacity, sensory characteristics, carbohydrate composition, or proximate nutrient content among the three pressure treatments. However, glucosinolate content in the root and nitrate concentration in the leaf declined as the atmospheric pressure decreased, suggesting perturbation to some nitrogen-related metabolism.

  8. Model of a stationary microwave argon discharge at atmospheric pressure

    SciTech Connect

    Zhelyazkov, I.; Pencheva, M.; Benova, E.

    2008-03-19

    The many applications of microwave gas discharges at atmospheric pressure in various fields of science, technology and medicine require an adequate model of these discharges. Such a model is based on the electromagnetic wave's propagation properties and on the elementary processes in the discharge bulk. In contrast to the microwave discharges at low-gas pressures, where many elementary processes might be ignored because of their negligible contribution to the electron and heavy particle's balance equations, for such discharges at atmospheric pressure the consideration of a large number of collisional processes is mandatory. For the build of a successful discharge-column model one needs three important quantities, notably the power {theta} necessary for sustaining an electron - ion pair, electron - neutral collision frequency for momentum transfer v{sub en}, and gas temperature T{sub g}. The first two key parameters are obtained by a collisional-radiative model of the argon at atmospheric pressure, while the microwave frequency {omega}/2{pi} = 2.45 GHz, plasma column radius R, gas pressure p and gas temperature T{sub g} are fixed external parameters determined by the experimental conditions. Here, we present a model of a capillary argon microwave plasma column with a length L {approx_equal} 14 cm, sustained by wave power of 110 W - the model yields the longitudinal distributions of the plasma density, expended wave power, wave electric field magnitude, and complex wave number.

  9. Ir/thz Double Resonance Signatures at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Phillips, Dane J.; Tanner, Elizabeth A.; Everitt, Henry O.; Medvedev, Ivan R.; Neese, Christopher F.; Holt, Jennifer; De Lucia, Frank C.

    2010-06-01

    IR/THz double resonance (DR) spectroscopy, historically used to investigate molecular collision dynamics and THz molecular lasers at low pressures (< 1 Torr), shows promise for trace gas remote sensing at atmospheric pressure. Molecular specificity is obtained through the rare coincidence(s) between molecule-specific ro-vibrational energy levels and CO2 laser lines. The resulting molecule-specific, DR-induced, THz spectroscopic signatures strongly depend on the type of ro-vibrational transition involved (P, Q, or R), the type of vibrational level excited (stretching or bending), and the molecular mass. To illustrate these sensitivities, calculated DR spectra of prototypical molecules such as methyl fluoride, methyl chloride, and methyl cyanide will be discussed. Although atmospheric pressure broadening obfuscates pure rotational spectra, we show how it can enhance the DR signature in two ways: by relaxing the pump coincidence requirement and by adding the DR signatures of multiple nearby transitions. We will present estimates of this enhancement, including cases where the coincidences that produce the strongest DR signatures at atmospheric pressure do not exist at low pressures.

  10. Diagnostics of transient non-equilibrium atmospheric pressure plasmas

    NASA Astrophysics Data System (ADS)

    Bruggeman, Peter

    2015-09-01

    Atmospheric pressure plasmas have received a renewed interest in last decades for a variety of applications ranging from environmental remediation, material processing and synthesis to envisioned medical applications such as wound healing. While most low pressure plasmas are diffuse, atmospheric pressure plasmas are often filamentary in nature. The existence of these filaments is correlated with strong gradients in plasma properties both in space and time that can significantly affect the plasma chemistry. As these filaments are often randomly appearing in space and time, it poses great challenges for diagnostics often requiring the stabilization of the filament to study the in situ plasma kinetics. In this contribution, diagnostics of a stabilized nanosecond pulsed plasma filament in a pin-pin geometry and a filament in a nanosecond pulsed atmospheric pressure plasma jet will be presented. We will focus on electron kinetics and OH and H radical production in water containing plasmas. The extension of these diagnostics to plasmas in liquids will also be discussed. The author acknowledges support from NSF PHYS1500135, Department of Energy Plasma Science Center through the U.S. Department of Energy, Office of Fusion Energy Sciences (Contract No. DE-SC0001939), University of Minnesota and STW (Netherlands).

  11. Stimulation of wound healing by helium atmospheric pressure plasma treatment

    NASA Astrophysics Data System (ADS)

    Vasile Nastuta, Andrei; Topala, Ionut; Grigoras, Constantin; Pohoata, Valentin; Popa, Gheorghe

    2011-03-01

    New experiments using atmospheric pressure plasma have found large application in treatment of living cells or tissues, wound healing, cancerous cell apoptosis, blood coagulation on wounds, bone tissue modification, sterilization and decontamination. In this study an atmospheric pressure plasma jet generated using a cylindrical dielectric-barrier discharge was applied for treatment of burned wounds on Wistar rats' skin. The low temperature plasma jet works in helium and is driven by high voltage pulses. Oxygen and nitrogen based impurities are identified in the jet by emission spectroscopy. This paper analyses the natural epithelization of the rats' skin wounds and two methods of assisted epithelization, a classical one using polyurethane wound dressing and a new one using daily atmospheric pressure plasma treatment of wounds. Systemic and local medical data, such as haematological, biochemical and histological parameters, were monitored during entire period of study. Increased oxidative stress was observed for plasma treated wound. This result can be related to the presence in the plasma volume of active species, such as O and OH radicals. Both methods, wound dressing and plasma-assisted epithelization, provided positive medical results related to the recovery process of burned wounds. The dynamics of the skin regeneration process was modified: the epidermis re-epitelization was accelerated, while the recovery of superficial dermis was slowed down.

  12. Model of a stationary microwave argon discharge at atmospheric pressure

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