WorldWideScience

Sample records for continuous gas-phase isopropylation

  1. Gas phase toluene isopropylation over high silica mordenite

    Indian Academy of Sciences (India)

    Sreedevi Upadhyayula

    2010-07-01

    Mordenite (HM) catalysts with three different Si/Al ratios were compared for their activity and selectivities in gas phase toluene isopropylation with isopropanol. Catalyst with Si/Al ratio 44.9 offered better cumene selectivity, hence, it was chosen for detailed kinetic investigations. The influence of various process parameters like temperature, time-on-stream, weight hourly space velocity (WHSV), reactant mole ratio on this catalyst activity are discussed. The cymene selectivity was found to increase with reaction temperature and passed through a maximum at 473 K. The deactivation with time-onstream is almost negligible. Lower isopropyl alcohol concentration in the feed improved cymene selectivity. The conversion and selectivity to cymenes were compared with those of the large pore beta catalyst. The rate constant and activation energy were found to be 7.34 m3/kg h and 41.84 kJ/mol, respectively using homogeneous kinetic model.

  2. Stabilized enzymes in continuous gas phase reactions

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Fangxiao; LeJeune, K.; Yang, Zhen [Univ. of Pittsburgh, PA (United States)] [and others

    1995-12-01

    We are assessing the utility of enzymes to catalyze reactions in a continuous gas phase reactor. First, alcohol dehydrogenase has been used to oxidize an unsaturated alcohol, 3-methyl-2-buten-1-ol (UOL), to the corresponding unsaturated aldehyde, 3-methyl-2-butenal (UAL). Cofactor NAD{sup +} was regenerated by concomitant acetone reduction to isopropyl alcohol. Second, organophosphorus hydrolase (OPH) has been used to hydrolyze pesticide vapors. In order to control enzyme hydration level, enzyme water adsorption isotherms at different temperature have been studied. Huttig`s isotherm model has been found suitable to describe adsorption behavior. The influence of enzyme hydration level, enzyme loading on glass beads, reaction temperature and flow rate on enzymatic reaction rate and biocatalyst stability were investigated. Reaction kinetics were studied and a kinetic model was proposed. We will also report our attempts to further stabilize enzymes for use in gas reactions by incorporating them into polymer matrices.

  3. Continuous-Flow Gas-Phase Bioreactors

    Science.gov (United States)

    Wise, Donald L.; Trantolo, Debra J.

    1994-01-01

    Continuous-flow gas-phase bioreactors proposed for biochemical, food-processing, and related industries. Reactor contains one or more selected enzymes dehydrated or otherwise immobilized on solid carrier. Selected reactant gases fed into reactor, wherein chemical reactions catalyzed by enzyme(s) yield product biochemicals. Concept based on discovery that enzymes not necessarily placed in traditional aqueous environments to function as biocatalysts.

  4. Continuous gas-phase synthesis of nanowires with tunable properties.

    Science.gov (United States)

    Heurlin, Magnus; Magnusson, Martin H; Lindgren, David; Ek, Martin; Wallenberg, L Reine; Deppert, Knut; Samuelson, Lars

    2012-12-06

    Semiconductor nanowires are key building blocks for the next generation of light-emitting diodes, solar cells and batteries. To fabricate functional nanowire-based devices on an industrial scale requires an efficient methodology that enables the mass production of nanowires with perfect crystallinity, reproducible and controlled dimensions and material composition, and low cost. So far there have been no reports of reliable methods that can satisfy all of these requirements. Here we show how aerotaxy, an aerosol-based growth method, can be used to grow nanowires continuously with controlled nanoscale dimensions, a high degree of crystallinity and at a remarkable growth rate. In our aerotaxy approach, catalytic size-selected Au aerosol particles induce nucleation and growth of GaAs nanowires with a growth rate of about 1 micrometre per second, which is 20 to 1,000 times higher than previously reported for traditional, substrate-based growth of nanowires made of group III-V materials. We demonstrate that the method allows sensitive and reproducible control of the nanowire dimensions and shape--and, thus, controlled optical and electronic properties--through the variation of growth temperature, time and Au particle size. Photoluminescence measurements reveal that even as-grown nanowires have good optical properties and excellent spectral uniformity. Detailed transmission electron microscopy investigations show that our aerotaxy-grown nanowires form along one of the four equivalent〈111〉B crystallographic directions in the zincblende unit cell, which is also the preferred growth direction for III-V nanowires seeded by Au particles on a single-crystal substrate. The reported continuous and potentially high-throughput method can be expected substantially to reduce the cost of producing high-quality nanowires and may enable the low-cost fabrication of nanowire-based devices on an industrial scale.

  5. Highly Selective Continuous Gas-Phase Methoxycarbonylation of Ethylene with Supported Ionic Liquid Phase (SILP) Catalysts

    DEFF Research Database (Denmark)

    Khokarale, Santosh Govind; Garcia Suárez, Eduardo José; Fehrmann, Rasmus

    2017-01-01

    Supported ionic liquid phase (SILP) technology was applied for the first time to the Pd-catalyzed continuous, gas-phase methoxycarbonylation of ethylene to selectively produce methyl propanoate (MP) in high yields. The influence of catalyst and reaction parameters such as, for example, ionic liqu...

  6. Supported Rh-phosphine complex catalysts for continuous gas-phase decarbonylation of aldehydes

    DEFF Research Database (Denmark)

    Malcho, Phillip; Garcia-Suarez, Eduardo J.; Mentzel, Uffe Vie;

    2014-01-01

    Heterogeneous silica supported rhodium-phosphine complex catalysts are employed for the first time in the catalytic decarbonylation of aldehydes in continuous gas-phase. The reaction protocol is exemplified for the decarbonylation of p-tolualdehyde to toluene and further extended to other aromatic...

  7. Continuous gas-phase hydroformylation of 1-butene using supported ionic liquid phase (SILP) catalysts

    DEFF Research Database (Denmark)

    Haumann, Marco; Dentler, Katharina; Joni, Joni;

    2007-01-01

    The concept of supported ionic liquid phase (SILP) catalysis has been extended to 1-butene hydroformylation. A rhodium-sulfoxantphos complex was dissolved in [BMIM][n-C8H17OSO3] and this solution was highly dispersed on silica. Continuous gas-phase experiments in a fixed-bed reactor revealed...

  8. Toward industrial scale synthesis of ultrapure singlet nanoparticles with controllable sizes in a continuous gas-phase process

    NARCIS (Netherlands)

    Feng, J.; Biskos, G.; Schmidt-Ott, A.

    2015-01-01

    Continuous gas-phase synthesis of nanoparticles is associated with rapid agglomeration, which can be a limiting factor for numerous applications. In this report, we challenge this paradigm by providing experimental evidence to support that gas-phase methods can be used to produce ultrapure nonagglom

  9. Continuous fixed-bed gas-phase hydroformylation using supported ionic liquid-phase (SILP) Rh catalysts

    DEFF Research Database (Denmark)

    Riisager, Anders; Wasserscheid, Peter; Van Hal, R.

    2003-01-01

    Continuous flow gas-phase hydroformylation of propene was performed using novel supported ionic liquid-phase (SILP) catalysts containing immobilized Rh complexes of the biphosphine ligand sulfoxantphos in the ionic liquids 1-n-butyl-3-methylimidazolium hexafluorophosphate and halogen-free 1-n......-butyl-3-methylimidazolium n-octylsulfate on silica support. The Rh-sulfoxantphos SILP catalysts proved to be more regioselective than catalysts without ligand and the analogous ionic liquid-free catalysts, giving up to 96% linear product. Furthermore, the performance of the catalysts was generally...

  10. Toward industrial scale synthesis of ultrapure singlet nanoparticles with controllable sizes in a continuous gas-phase process

    Science.gov (United States)

    Feng, Jicheng; Biskos, George; Schmidt-Ott, Andreas

    2015-10-01

    Continuous gas-phase synthesis of nanoparticles is associated with rapid agglomeration, which can be a limiting factor for numerous applications. In this report, we challenge this paradigm by providing experimental evidence to support that gas-phase methods can be used to produce ultrapure non-agglomerated “singlet” nanoparticles having tunable sizes at room temperature. By controlling the temperature in the particle growth zone to guarantee complete coalescence of colliding entities, the size of singlets in principle can be regulated from that of single atoms to any desired value. We assess our results in the context of a simple analytical model to explore the dependence of singlet size on the operating conditions. Agreement of the model with experimental measurements shows that these methods can be effectively used for producing singlets that can be processed further by many alternative approaches. Combined with the capabilities of up-scaling and unlimited mixing that spark ablation enables, this study provides an easy-to-use concept for producing the key building blocks for low-cost industrial-scale nanofabrication of advanced materials.

  11. Toward industrial scale synthesis of ultrapure singlet nanoparticles with controllable sizes in a continuous gas-phase process.

    Science.gov (United States)

    Feng, Jicheng; Biskos, George; Schmidt-Ott, Andreas

    2015-10-29

    Continuous gas-phase synthesis of nanoparticles is associated with rapid agglomeration, which can be a limiting factor for numerous applications. In this report, we challenge this paradigm by providing experimental evidence to support that gas-phase methods can be used to produce ultrapure non-agglomerated "singlet" nanoparticles having tunable sizes at room temperature. By controlling the temperature in the particle growth zone to guarantee complete coalescence of colliding entities, the size of singlets in principle can be regulated from that of single atoms to any desired value. We assess our results in the context of a simple analytical model to explore the dependence of singlet size on the operating conditions. Agreement of the model with experimental measurements shows that these methods can be effectively used for producing singlets that can be processed further by many alternative approaches. Combined with the capabilities of up-scaling and unlimited mixing that spark ablation enables, this study provides an easy-to-use concept for producing the key building blocks for low-cost industrial-scale nanofabrication of advanced materials.

  12. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 2 covers the advances in gas phase ion chemistry. The book discusses the stabilities of positive ions from equilibrium gas-phase basicity measurements; the experimental methods used to determine molecular electron affinities, specifically photoelectron spectroscopy, photodetachment spectroscopy, charge transfer, and collisional ionization; and the gas-phase acidity scale. The text also describes the basis of the technique of chemical ionization mass spectrometry; the energetics and mechanisms of unimolecular reactions of positive ions; and the photodissociation

  13. Nanopaper based on Ag/TiO{sub 2} nanobelts heterostructure for continuous-flow photocatalytic treatment of liquid and gas phase pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Weijia; Du, Guojun; Hu, Peiguang [State Key Laboratory of Crystal Materials, Center of Bio and Micro/Nano Functional Materials, Shandong University, 27 Shandanan Road, Jinan 250100 (China); Yin, Yongquan [The School of Environmental Science and Engineering, Shandong University, 27 Shandanan Road, Jinan 250100 (China); Li, Jianhua [State Key Laboratory of Crystal Materials, Center of Bio and Micro/Nano Functional Materials, Shandong University, 27 Shandanan Road, Jinan 250100 (China); Yu, Jiahong [The School of Environmental Science and Engineering, Shandong University, 27 Shandanan Road, Jinan 250100 (China); Wang, Guancong [State Key Laboratory of Crystal Materials, Center of Bio and Micro/Nano Functional Materials, Shandong University, 27 Shandanan Road, Jinan 250100 (China); Wang, Jinxia [School of Light Chemistry and Environment Engineering, Shandong Polytechnic University, Daxue Road, Western University Science Park, Jinan 250353 (China); Liu, Hong, E-mail: hongliu@sdu.edu.cn [State Key Laboratory of Crystal Materials, Center of Bio and Micro/Nano Functional Materials, Shandong University, 27 Shandanan Road, Jinan 250100 (China); Wang, Jiyang, E-mail: jywang@icm.sdu.edu.cn [State Key Laboratory of Crystal Materials, Center of Bio and Micro/Nano Functional Materials, Shandong University, 27 Shandanan Road, Jinan 250100 (China); Zhang, Hua [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore)

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer The photocatalytic activity of TiO{sub 2} nanobelts is evidently enhanced by the heterostructures between Ag nanoparticles and TiO{sub 2} nanobelts. Black-Right-Pointing-Pointer The nanopapers based on Ag/TiO{sub 2} nanobelt heterostructures are fabricated via a modified paper-making process. Black-Right-Pointing-Pointer A continuous flow photocatalytic reactor is designed. Black-Right-Pointing-Pointer The TiO{sub 2} nanopapers in the microreactor show an excellent continuous photocatalytic performance for liquid and gas phase pollutants. Black-Right-Pointing-Pointer The Ag/TiO{sub 2} nanobelts nanopaper shows a good antibacterial effect. - Abstract: The Ag/TiO{sub 2} nanobelt heterostructures were prepared by the acid-assisted hydrothermal method followed by an in situ photo-reduction process. The photocatalytic activity of TiO{sub 2} nanobelts was evidently enhanced by the heterostructures between Ag nanoparticles and TiO{sub 2} nanobelts. The nanopapers based on Ag/TiO{sub 2} nanobelt heterostructures were fabricated via a modified paper-making process. A novel continuous photocatalytic reactor was designed, and MO removal rate of Ag/C-TiO{sub 2} nanopaper was achieved to 100% in 40 min for single layer and only in 6 min for three layers. The self-supported TiO{sub 2} nanopapers with porous structures also showed an excellent continuous photocatalytic performance for toluene gas under UV light irradiation, and the corresponding degradation rate was 69.5% in 184 min. Moreover, the Ag/TiO{sub 2} nanobelts nanopaper showed a good antibacterial effect. The multifunctional TiO{sub 2} nanopapers modified by the heterostuctures could have potential applications in the environmental and biomaterial fields.

  14. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 1 covers papers on the advances of gas phase ion chemistry. The book discusses the advances in flow tubes and the measurement of ion-molecule rate coefficients and product distributions; the ion chemistry of the earth's atmosphere; and the classical ion-molecule collision theory. The text also describes statistical methods in reaction dynamics; the state selection by photoion-photoelectron coincidence; and the effects of temperature and pressure in the kinetics of ion-molecule reactions. The energy distribution in the unimolecular decomposition of ions, as well

  15. Gas-Phase Thermolyses

    DEFF Research Database (Denmark)

    Carlsen, Lars; Egsgaard, Helge

    1982-01-01

    The unimolecular gas-phase thermolyses of 1,2,3-oxadithiolan 2-oxide and thiiran 1-oxide have been studied by the flash vacuum thermolysis–field ionization mass spectrometry (f.v.t.–f.i.m.s.) technique in the temperature range from 1 043 to 1 404 K. The reactions are rationalized in terms...

  16. Gas-Phase Thermolyses

    DEFF Research Database (Denmark)

    Carlsen, Lars; Egsgaard, Helge

    1982-01-01

    The unimolecular gas-phase thermolyses of the four methyl and ethyl monothioacetates (5)–(8) have been studied by the flash vacuum thermolysis–field ionization mass spectrometry technique in the temperature range 883–1 404 K. The types of reactions verified were keten formation, thiono...

  17. Gas-Phase Thermolysis

    DEFF Research Database (Denmark)

    Carlsen, Lars; Egsgaard, Helge; Schaumann, Ernst

    1980-01-01

    The unimolecular gas-phase thermolytic decomposition of three silylated thionocarboxylic acid derivatives (2b), (3), and (8) have been studied by the flash vacuum thermolysis–field ionization mass spectrometry technique in the temperature range from 783 to 1 404 K in order to elucidate its possib...

  18. Oxidation state-differentiated measurement of aqueous inorganic arsenic by continuous flow electrochemical arsine generation coupled to gas-phase chemiluminescence detection.

    Science.gov (United States)

    Sengupta, Mrinal K; Dasgupta, Purnendu K

    2011-12-15

    The electrochemical reduction of inorganic As on a graphite cathode depends on the current density. We observed that while only inorganic As(III) is reduced to AsH(3) at low current densities, at high current densities both forms of inorganic As are reduced. We describe a unique electrochemical reactor in which the cylindrical anode compartment is isolated from the outer concentric cathode compartment by a Nafion tube in which a hole is deliberately made and the entire anode compartment is inside the cylindrical cavity of a small volume (∼115 μL) cathode chamber. The evolved arsine is then quantitated by gas-phase chemiluminescence (GPCL) reaction with ozone; the latter is generated from oxygen formed during electrolysis. For the dimensions used, inorganic As(III) can be selectively determined at a current of 0.1 A while total inorganic As (both As(III) and As(V)) respond equally at an applied electrolysis current at 0.85 A, without any sample treatment. For a 1-mL sample, the system provides a limit of detection (LOD, S/N = 3) of 0.09 μg/L for total As (i = 0.85 A) and an LOD of 0.76 μg/L for As(III) (i = 0.10 A); As(V) is obtained by difference. Comparison of ICP-MS results for total As in groundwater samples that span a large range of concentration and total inorganic As determined by the present method showed a high correlation (r(2) = 0.9975) and a near unity slope. The basic electrochemical arsine generation technique and current-differentiated oxidation state speciation should be applicable as the front end to many other arsenic measurements techniques, including atomic spectrometry.

  19. Gas-phase chemical dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Weston, R.E. Jr.; Sears, T.J.; Preses, J.M. [Brookhaven National Laboratory, Upton, NY (United States)

    1993-12-01

    Research in this program is directed towards the spectroscopy of small free radicals and reactive molecules and the state-to-state dynamics of gas phase collision, energy transfer, and photodissociation phenomena. Work on several systems is summarized here.

  20. Gas phase grown silicon germanium nanocrystals

    Science.gov (United States)

    Mohan, A.; Tichelaar, F. D.; Kaiser, M.; Verheijen, M. A.; Schropp, R. E. I.; Rath, J. K.

    2016-09-01

    We report on the gas phase synthesis of highly crystalline and homogeneously alloyed Si1-xGex nanocrystals in continuous and pulsed plasmas. Agglomerated nanocrystals have been produced with remarkable control over their composition by altering the precursor GeH4 gas flow in a continuous plasma. We specially highlight that in the pulsed plasma mode, we obtain quantum-sized free standing alloy nanocrystals with a mean size of 7.3 nm. The presence of Si1-xGex alloy particles is confirmed with multiple techniques, i.e. Raman spectroscopy, XRD (Xray diffraction) and HRTEM (high resolution transmission electron microscopy) studies, with each of these methods consistently yielding the same composition. The nanocrystals synthesized here have potential applications in band-gap engineering for multijunction solar cells.

  1. Gas Phase Hydration of Methyl Glyoxal to Form the Gemdiol

    Science.gov (United States)

    Kroll, Jay A.; Axson, Jessica L.; Vaida, Veronica

    2016-06-01

    Methylglyoxal is a known oxidation product of volatile organic compounds (VOCs) in Earth's atmosphere. While the gas phase chemistry of methylglyoxal is fairly well understood, its modeled concentration and role in the formation of secondary organic aerosol (SOA) continues to be controversial. The gas phase hydration of methylglyoxal to form a gemdiol has not been widely considered for water-restricted environments such as the atmosphere. However, this process may have important consequences for the atmospheric processing of VOCs. We will report on spectroscopic work done in the Vaida laboratory studying the hydration of methylglyoxal and discuss the implications for understanding the atmospheric processing and fate of methylglyoxal and similar molecules.

  2. Gas Phase Sulfur, Chlorine and Potassium Chemistry in Biomass Combustion

    DEFF Research Database (Denmark)

    Løj, Lusi Hindiyarti

    2007-01-01

    conditions. These trace species contained in the biomass structure will be released to the gas phase during combustion and contribute to the problems generated during the process. The investigation during this PhD project is done to stepwise improve the understanding in the chemistry and reduce...... the uncertainties. In the present work, the detailed kinetic model for gas phase sulfur, chlorine, alkali metal, and their interaction has been updated. The K/O/H/Cl chemistry, S chemistry, and their interaction can reasonably predict a range of experimental data. In general, understanding of the interaction......Gas Phase Sulfur, Chlorine and Alkali Metal Chemistry in Biomass Combustion Concern about aerosols formation, deposits, corrosion, and gaseous emissions during biomass combustion, especially straw, continues to be a driving force for investigation on S, Cl, K-containing species under combustions...

  3. Precursor-Less Coating of Nanoparticles in the Gas Phase

    NARCIS (Netherlands)

    Pfeiffer, T.V.; Kedia, P.; Messing, M.E.; Valvo, M.; Schmidt-Ott, A.

    2015-01-01

    This article introduces a continuous, gas-phase method for depositing thin metallic coatings onto (nano)particles using a type of physical vapor deposition (PVD) at ambient pressure and temperature. An aerosol of core particles is mixed with a metal vapor cloud formed by spark ablation by passing th

  4. 21 CFR 173.240 - Isopropyl alcohol.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Isopropyl alcohol. 173.240 Section 173.240 Food and..., Lubricants, Release Agents and Related Substances § 173.240 Isopropyl alcohol. Isopropyl alcohol may be... label of the hops extract specifies the presence of the isopropyl alcohol and provides for the use...

  5. Flourescence from Gas-Phase Biomolecular Ions

    DEFF Research Database (Denmark)

    2013-01-01

    difficulties, of fluorescence spectroscopy compared to absorption spectroscopy are discussed. Extensive work has been done on the isolated dyes in characterising them with respect to their dispersed fluorescence spectra, excited-state lifetimes, and gas-phase Stokes shifts. After a brief introduction, results...

  6. Thermal stability of gas phase magnesium nanoparticles

    NARCIS (Netherlands)

    Krishnan, Gopi; Kooi, Bart J.; Palasantzas, George; Pivak, Yevheniy; Dam, Bernard

    2010-01-01

    In this work we present a unique transmission electron microscopy study of the thermal stability of gas phase synthesized Mg nanoparticles, which have attracted strong interest as high capacity hydrogen storage materials. Indeed, Mg nanoparticles with a MgO shell (similar to 3 nm thick) annealed at

  7. Thermal stability of gas phase magnesium nanoparticles

    NARCIS (Netherlands)

    Krishnan, G.; Kooi, B.J.; Palasantzas, G.; Pivak, Y.; Dam, B.

    2010-01-01

    In this work we present a unique transmission electron microscopy study of the thermal stability of gas phase synthesized Mg nanoparticles, which have attracted strong interest as high capacity hydrogen storage materials. Indeed, Mg nanoparticles with a MgO shell ( ∼ 3 nm thick) annealed at 300 °C

  8. Thermal stability of gas phase magnesium nanoparticles

    NARCIS (Netherlands)

    Krishnan, G.; Kooi, B.J.; Palasantzas, G.; Pivak, Y.; Dam, B.

    2010-01-01

    In this work we present a unique transmission electron microscopy study of the thermal stability of gas phase synthesized Mg nanoparticles, which have attracted strong interest as high capacity hydrogen storage materials. Indeed, Mg nanoparticles with a MgO shell ( ∼ 3 nm thick) annealed at 300 °C s

  9. Gas-Phase Infrared; JCAMP Format

    Science.gov (United States)

    SRD 35 NIST/EPA Gas-Phase Infrared; JCAMP Format (PC database for purchase)   This data collection contains 5,228 infrared spectra in the JCAMP-DX (Joint Committee for Atomic and Molecular Physical Data "Data Exchange") format.

  10. Gas-Phase Reactivity of Microsolvated Anions

    DEFF Research Database (Denmark)

    Thomsen, Ditte Linde

    Gas-phase studies of ion-molecule reactions shed light on the intrinsic factors that govern reactivity; and even solvent effects can be examined in the gasphase environment by employing microsolvated ions. An area that has received considerable attention with regard to the interplay between...... intrinsic factors and solvent effects is the enhanced reactivity of α-nucleophiles – nucleophiles with a lone-pair adjacent to the attacking site – referred to as the α-effect. This thesis concerns the reactivity of microsolvated anions and in particular how the presence of a single solvent molecule affects...... the gas-phase α-effect. The experimental studies are performed by means of the flowing after glow selected ion flow tube technique, and these are supplemented by electronic structure calculations. The α-nucleophile employed is the microsolvated hydrogen peroxide anion whose reactivity is compared...

  11. Liquid gas phase transition in hypernuclei

    CERN Document Server

    Mallik, S

    2016-01-01

    The fragmentation of excited hypernuclear system formed in heavy ion collisions has been described by the canonical thermodynamical model extended to three component systems. The multiplicity distribution of the fragments has been analyzed in detail and it has been observed that the hyperons have the tendency to get attached to the heavier fragments. Another important observation is the phase coexistence of the hyperons, a phenomenon which is linked to liquid gas phase transition in strange matter.

  12. Catalytic Synthesis of Isopropyl Benzene over SO42-/ZrO2 -MCM-41

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Super acid catalyst SO2-4-/ZrO2 was introduced into pure silicone MCM-41 via the impregnation method and the catalyst samples obtained at different temperatures were characterized by means of XRD, IR, and Py-IR techniques.The selectively catalytic gas-phase flow reactions of benzene with propene over the catalyst samples were carried out in a made-to-measure high-pressure flow reactor equipped with a thermostat and a condenser. Effect of the preparative condition on the catalytic synthesis of isopropyl benzene over the catalyst samples was tested. The results show that SO2-4/ZrO2-MCM-41 (SZM-41) can be used as a catalyst for the title reaction, in which there are a higher conversion (97%) for the propene and a higher selectivity(93%) for the isopropyl benzene.

  13. Receptors useful for gas phase chemical sensing

    Energy Technology Data Exchange (ETDEWEB)

    Jaworski, Justyn W; Lee, Seung-Wuk; Majumdar, Arunava; Raorane, Digvijay A

    2015-02-17

    The invention provides for a receptor, capable of binding to a target molecule, linked to a hygroscopic polymer or hydrogel; and the use of this receptor in a device for detecting the target molecule in a gaseous and/or liquid phase. The invention also provides for a method for detecting the presence of a target molecule in the gas phase using the device. In particular, the receptor can be a peptide capable of binding a 2,4,6-trinitrotoluene (TNT) or 2,4,-dinitrotoluene (DNT).

  14. Gas phase reactive collisions, experimental approach

    Directory of Open Access Journals (Sweden)

    Canosa A.

    2012-01-01

    Full Text Available Since 1937 when the first molecule in space has been identified, more than 150 molecules have been detected. Understanding the fate of these molecules requires having a perfect view of their photochemistry and reactivity with other partners. It is then crucial to identify the main processes that will produce and destroy them. In this chapter, a general view of experimental techniques able to deliver gas phase chemical kinetics data at low and very low temperatures will be presented. These techniques apply to the study of reactions between neutral reactants on the one hand and reactions involving charge species on the other hand.

  15. Gas phase thermochemistry of organogermanium compounds

    Energy Technology Data Exchange (ETDEWEB)

    Engel, J.P.

    1993-12-07

    A variety of silyl- and alkyl-germylene precursors have been synthesized and subsequently pyrolyzed in the gas phase. Arrhenius parameters were obtained employing a pulsed-stirred flow reactor for these unimolecular decompositions. These precursors are divided into two major categories by mechanism of germylene extrusion: {alpha}-elimination precursors and germylacetylenes. The extrusion of germylenes from germylacetylene precursors is of primary interest. A mechanism is proposed employing a germacyclopropene intermediate. Evidence supporting this mechanism is presented. In the process of exploring germylacetylenes as germylene precursors, an apparent dyatropic rearrangement between germanium and silicon was observed. This rearrangement was subsequently explored.

  16. Amperometric sensing in the gas-phase

    Energy Technology Data Exchange (ETDEWEB)

    Knake, Rene [University of Basel, Department of Chemistry, Spitalstrasse 51, 4004 Basel (Switzerland); Jacquinot, Patrick [University of Basel, Department of Chemistry, Spitalstrasse 51, 4004 Basel (Switzerland); Hodgson, Alexia W.E. [University of Basel, Department of Chemistry, Spitalstrasse 51, 4004 Basel (Switzerland); Hauser, Peter C. [University of Basel, Department of Chemistry, Spitalstrasse 51, 4004 Basel (Switzerland)]. E-mail: peter.hauser@unibas.ch

    2005-09-06

    The design of amperometric sensors for gaseous species presents a challenge as the gas phase has to be brought into contact with a solid electrode as well as an electrolyte phase which usually is liquid. However, many species of analytical interest are electroactive, such as SO{sub 2}, NO {sub x}, O{sub 3}, CO, formaldehyde or ethanol, and electrochemical means are always attractive in designing sensors because the electronic signal is obtained directly. Therefore, different approaches have been implemented and some types of such sensors have been available commercially for quite some time. Nevertheless, many new developments with regard to an improvement of sensitivity, selectivity and in the construction of these devices have been reported over the last few years, as well as approaches to miniaturization. In this review it is attempted to give an overview of the state of the art of this field, highlighting recent developments.

  17. Gas-Phase Reactivity of Microsolvated Anions

    DEFF Research Database (Denmark)

    Thomsen, Ditte Linde

    intrinsic factors and solvent effects is the enhanced reactivity of α-nucleophiles – nucleophiles with a lone-pair adjacent to the attacking site – referred to as the α-effect. This thesis concerns the reactivity of microsolvated anions and in particular how the presence of a single solvent molecule affects...... the gas-phase α-effect. The experimental studies are performed by means of the flowing after glow selected ion flow tube technique, and these are supplemented by electronic structure calculations. The α-nucleophile employed is the microsolvated hydrogen peroxide anion whose reactivity is compared...... to that of a series of microsolvated oxygen centered anions. The association of the nucleophiles with a single water or methanol molecule allows the α-effect to be observed in the SN2 reaction with methyl chloride; this effect was not apparent in the reactions of the unsolvated anions. The results suggest...

  18. Fundamentals of gas phase plasmas for treatment of human tissue.

    Science.gov (United States)

    Kushner, Mark J; Babaeva, Natalia Yu

    2011-01-01

    The use of gas phase plasmas for treating human tissue is at the intersection of two disciplines - plasma physics and engineering, and medicine. In this paper, a primer will be provided for the medical practitioner on the fundamentals of generating gas phase plasmas at atmospheric pressure in air for the treatment of human tissue. The mechanisms for gas phase plasmas interacting with tissue and biological fluids will also be discussed using results from computer modeling.

  19. Gas-phase advanced oxidation for effective, efficient in situ control of pollution

    DEFF Research Database (Denmark)

    Johnson, Matthew Stanley; Nilsson, Elna Johanna Kristina; Svensson, Erik Anders

    2014-01-01

    In this article, gas-phase advanced oxidation, a new method for pollution control building on the photo-oxidation and particle formation chemistry occurring in the atmosphere, is introduced and characterized. The process uses ozone and UV-C light to produce in situ radicals to oxidize pollution....... The laboratory prototype was built of standard ventilation duct and could treat up to 850 m3/h. A portable continuous-flow prototype built in an aluminum flight case was able to treat 46 m3/h. Removal efficiencies of >95% were observed for propane, cyclohexane, benzene, isoprene, aerosol particle mass, and ozone...... on these results, in situ gas-phase advanced oxidation is a viable control strategy for most volatile organic compounds, specifically those with a OH* reaction rate higher than ca. 5 × 10-13 cm3/s. Gas-phase advanced oxidation is able to remove compounds that react with OH and to control ozone and total...

  20. Hydrocarbon radical thermochemistry: Gas-phase ion chemistry techniques

    Energy Technology Data Exchange (ETDEWEB)

    Ervin, Kent M. [Univ. of Nevada, Reno, NV (United States)

    2014-03-21

    Final Scientific/Technical Report for the project "Hydrocarbon Radical Thermochemistry: Gas-Phase Ion Chemistry Techniques." The objective of this project is to exploit gas-phase ion chemistry techniques for determination of thermochemical values for neutral hydrocarbon radicals of importance in combustion kinetics.

  1. Gas-phase infrared photodissociation spectroscopy of cationic polyaromatic hydrocarbons

    NARCIS (Netherlands)

    Oomens, J.; van Roij, A. J. A.; Meijer, G.; von Helden, G.

    2000-01-01

    Infrared spectra of gas-phase cationic naphthalene, phenanthrene, anthracene, and pyrene are recorded in the 500-1600 cm(-1) range using multiphoton dissociation in an ion trap. Gas-phase polyaromatic hydrocarbons are photoionized by an excimer laser and stored in a quadrupole ion trap. Subsequent i

  2. 27 CFR 21.113 - Isopropyl alcohol.

    Science.gov (United States)

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Isopropyl alcohol. 21.113 Section 21.113 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS FORMULAS FOR DENATURED ALCOHOL AND RUM Specifications for Denaturants §...

  3. Catalytic Performance of Al-MCM-48 Molecular Sieves for Isopropylation of Phenol with Isopropyl Acetate

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Al-MCM-48 molecular sieves (Si/Al molar ratios = 25, 50, 75, and 100) were synthesized hydrothermally using cetyltrimethyl-ammonium bromide as the structure directing template. The orderly arrangement of mesopores was evident from the low angle X-ray diffraction patterns and transmission electron microscopy images. The catalytic performance of the materials was evaluated in the vapor phase isopropylation of phenol with isopropyl acetate. Phenol conversion decreased with the increase in the Si/Al ratio of the catalysts. The major reaction product was 4-isopropyl phenol with 78% selectivity. The delocalization of phenolic oxygen electron pair over the aromatic ring promoted para-selective alkylation. Such delocalization could be aided by the hydrophilic surface of the molecular sieves. Although an ester was used as the alkylating agent, phenyl isopropyl ether was not formed in the reaction.

  4. Liquid-Gas Phase Transition in Nuclear Equation of State

    CERN Document Server

    Lee, S J

    1997-01-01

    A canonical ensemble model is used to describe a caloric curve of nuclear liquid-gas phase transition. Allowing a discontinuity in the freeze out density from one spinodal density to another for a given initial temperature, the nuclear liquid-gas phase transition can be described as first order. Averaging over various freeze out densities of all the possible initial temperatures for a given total reaction energy, the first order characteristics of liquid-gas phase transition is smeared out to a smooth transition. Two experiments, one at low beam energy and one at high beam energy show different caloric behaviors and are discussed.

  5. Clean and highly ordered graphene synthesized in the gas phase.

    Science.gov (United States)

    Dato, Albert; Lee, Zonghoon; Jeon, Ki-Joon; Erni, Rolf; Radmilovic, Velimir; Richardson, Thomas J; Frenklach, Michael

    2009-10-28

    We report that the substrate-free gas-phase graphene synthesis method produces clean and highly ordered graphene sheets that are similar in quality to the graphene obtained through the mechanical exfoliation of highly oriented pyrolytic graphite.

  6. Precursor-Less Coating of Nanoparticles in the Gas Phase

    Directory of Open Access Journals (Sweden)

    Tobias V. Pfeiffer

    2015-03-01

    Full Text Available This article introduces a continuous, gas-phase method for depositing thin metallic coatings onto (nanoparticles using a type of physical vapor deposition (PVD at ambient pressure and temperature. An aerosol of core particles is mixed with a metal vapor cloud formed by spark ablation by passing the aerosol through the spark zone using a hollow electrode configuration. The mixing process rapidly quenches the vapor, which condenses onto the core particles at a timescale of several tens of milliseconds in a manner that can be modeled as bimodal coagulation. Gold was deposited onto core nanoparticles consisting of silver or polystyrene latex, and silver was deposited onto gold nanoparticles. The coating morphology depends on the relative surface energies of the core and coating materials, similar to the growth mechanisms known for thin films: a coating made of a substance having a high surface energy typically results in a patchy coverage, while a coating material with a low surface energy will normally “wet” the surface of a core particle. The coated particles remain gas-borne, allowing further processing.

  7. Gas-phase metalloprotein complexes interrogated by ion mobility-mass spectrometry

    Science.gov (United States)

    Faull, Peter A.; Korkeila, Karoliina E.; Kalapothakis, Jason M.; Gray, Andrew; McCullough, Bryan J.; Barran, Perdita E.

    2009-06-01

    Gas-phase biomolecular structure may be explored through a number of analytical techniques. Ion mobility-mass spectrometry (IM-MS) continues to prove itself as a sensitive and reliable bioanalytical tool for gas-phase structure determination due to intense study and development over the past 15 years. A vast amount of research interest, especially in protein and peptide conformational studies has generated a wealth of structural information for biological systems from small peptides to megadalton-sized biomolecules. In this work, linear low field IM-MS has been used to study gas-phase conformations and determine rotationally averaged collision cross-sections of three metalloproteins--cytochrome c, haemoglobin and calmodulin. Measurements have been performed on the MoQToF, a modified QToF 1 instrument (Micromass UK Ltd., Manchester, UK) modified in house. Gas-phase conformations and cross-sections of multimeric cytochrome c ions of the form [xM + nH+]n+ for x = 1-3 (monomer to trimer) have been successfully characterised and measured. We believe these to be the first reported collision cross-sections of higher order multimeric cytochrome c. Haemoglobin is investigated to obtain structural information on the associative mechanism of tetramer formation. Haemoglobin molecules, comprising apo- and holo-monomer chains, dimer and tetramer are transferred to the gas phase under a range of solution conditions. Structural information on the proposed critical intermediate, semi-haemoglobin, is reported. Cross-sections of the calcium binding protein calmodulin have been obtained under a range of calcium-bound conditions. Metalloprotein collision cross-sections from ion mobility measurements are compared with computationally derived values from published NMR and X-ray crystallography structural data. Finally we consider the change in the density of the experimentally measured rotationally averaged collision cross-section for compact geometries of the electrosprayed proteins.

  8. Isopropyl alcohol recovery by heteroazeotropic batch distillation

    OpenAIRE

    Van Baelen, Guy; Vreysen, Steven; Gerbaud, Vincent; Rodriguez-Donis, Ivonne; Geens, Jeroen; Janssens, Bart

    2010-01-01

    Solvent recovery is becoming a major issue in the pharmaceutical and specialty chemical industries. Solvent recovery by conventional batch distillation is limited by the frequent presence of azeotropes in the used solvent mixtures. Most distillation processes for the separation of azeotropic or difficult zeotropic mixtures involve the addition of an entrainer (homogeneous and heterogeneous azeotropic distillation or extractive distillation). In this study the recovery of IPA (isopropyl alc...

  9. Gas phase metal cluster model systems for heterogeneous catalysis.

    Science.gov (United States)

    Lang, Sandra M; Bernhardt, Thorsten M

    2012-07-14

    Since the advent of intense cluster sources, physical and chemical properties of isolated metal clusters are an active field of research. In particular, gas phase metal clusters represent ideal model systems to gain molecular level insight into the energetics and kinetics of metal-mediated catalytic reactions. Here we summarize experimental reactivity studies as well as investigations of thermal catalytic reaction cycles on small gas phase metal clusters, mostly in relation to the surprising catalytic activity of nanoscale gold particles. A particular emphasis is put on the importance of conceptual insights gained through the study of gas phase model systems. Based on these concepts future perspectives are formulated in terms of variation and optimization of catalytic materials e.g. by utilization of bimetals and metal oxides. Furthermore, the future potential of bio-inspired catalytic material systems are highlighted and technical developments are discussed.

  10. Oscillatory burning of solid propellants including gas phase time lag.

    Science.gov (United States)

    T'Ien, J. S.

    1972-01-01

    An analysis has been performed for oscillatory burning of solid propellants including gas phase time lag. The gaseous flame is assumed to be premixed and laminar with a one-step overall chemical reaction. The propellant is assumed to decompose according to the Arrenhius Law, with no condensed phase reaction. With this model, strong gas phase resonance has been found in certain cases at the characteristic gas-phase frequencies, but the peaking of the acoustic admittance is in the direction favoring the damping of pressure waves. At still higher frequencies, moderate wave-amplifying ability was found. The limit of low frequency response obtained previously by Denison and Baum was recovered, and the limitations of the quasi-steady theory were investigated.

  11. Effect of counter current gas phase on liquid film

    Institute of Scientific and Technical Information of China (English)

    Shujuan LUO; Huaizhi LI; Weiyang FEI; Yundong WANG

    2009-01-01

    Liquid film flow is very important in many industrial applications. However, there are few reports about its characteristics on structured packings. Therefore, in this paper, liquid film phenomena were investigated experimentally to exploit new approaches for intensifying the performance of the structured packings. All experiments were performed at room temperature. Water and air were the working fluids. The effect of counter current gas phase on the liquid film was taken into consideration. A high speed camera, a non-intrusive measurement technique, was used. It is shown that both liquid and gas phases have strong effects on film characteristics. In the present work, liquid film width increased by 57% because of increasing liquid flow rate, while it decreased by 25% resulting from the counter current gas phase.

  12. Oscillatory burning of solid propellants including gas phase time lag.

    Science.gov (United States)

    T'Ien, J. S.

    1972-01-01

    An analysis has been performed for oscillatory burning of solid propellants including gas phase time lag. The gaseous flame is assumed to be premixed and laminar with a one-step overall chemical reaction. The propellant is assumed to decompose according to the Arrenhius Law, with no condensed phase reaction. With this model, strong gas phase resonance has been found in certain cases at the characteristic gas-phase frequencies, but the peaking of the acoustic admittance is in the direction favoring the damping of pressure waves. At still higher frequencies, moderate wave-amplifying ability was found. The limit of low frequency response obtained previously by Denison and Baum was recovered, and the limitations of the quasi-steady theory were investigated.

  13. Post-flame gas-phase sulfation of potassium chloride

    DEFF Research Database (Denmark)

    Li, Bo; Sun, Zhiwei; Li, Zhongshan;

    2013-01-01

    homogeneous systems are required to characterize the gas-phase formation of alkali sulfates. We have measured the temperature and gas-phase concentrations of KCl and HCl, and detected the presence of aerosols in the post-flame region of a range of hydrocarbon flames seeded with KCl, with and without......The sulfation of KCl during biomass combustion has implications for operation and emissions: it reduces the rates of deposition and corrosion, it increases the formation of aerosols, and it leads to higher concentrations of HCl and lower concentrations of SO2 in the gas phase. Rigorously...... the addition of SO2. Dilution of the flame products with different amounts of N2 ensured post-flame temperatures in the range 950–1400K. In the absence of SO2, KCl levels were constant in the post-flame zone and no aerosols were formed, even at the lowest temperatures. In the presence of SO2, KCl was consumed...

  14. Negative ion gas-phase chemistry of arenes.

    Science.gov (United States)

    Danikiewicz, Witold; Zimnicka, Magdalena

    2016-01-01

    Reactions of aromatic and heteroaromatic compounds involving anions are of great importance in organic synthesis. Some of these reactions have been studied in the gas phase and are occasionally mentioned in reviews devoted to gas-phase negative ion chemistry, but no reviews exist that collect all existing information about these reactions. This work is intended to fill this gap. In the first part of this review, methods for generating arene anions in the gas phase and studying their physicochemical properties and fragmentation reactions are presented. The main topics in this part are as follows: processes in which gas-phase arene anions are formed, measurements and calculations of the proton affinities of arene anions, proton exchange reactions, and fragmentation processes of substituted arene anions, especially phenide ions. The second part is devoted to gas-phase reactions of arene anions. The most important of these are reactions with electrophiles such as carbonyl compounds and α,β-unsaturated carbonyl and related compounds (Michael acceptors). Other reactions including oxidation of arene anions and halogenophilic reactions are also presented. In the last part of the review, reactions of electrophilic arenes with nucleophiles are discussed. The best known of these is the aromatic nucleophilic substitution (SN Ar) reaction; however, other processes that lead to the substitution of a hydrogen atom in the aromatic ring are also very important. Aromatic substrates in these reactions are usually but not always nitroarenes bearing other substituents in the ring. The first step in these reactions is the formation of an anionic σ-adduct, which, depending on the substituents in the aromatic ring and the structure of the attacking nucleophile, is either an intermediate or a transition state in the reaction path. In the present review, we attempted to collect the results of both experimental and computational studies of the aforementioned reactions conducted since the

  15. Reactive intermediates in the gas phase generation and monitoring

    CERN Document Server

    Setser, D W

    2013-01-01

    Reactive Intermediates in the Gas Phase: Generation and Monitoring covers methods for reactive intermediates in the gas phase. The book discusses the generation and measurement of atom and radical concentrations in flow systems; the high temperature flow tubes, generation and measurement of refractory species; and the electronically excited long-lived states of atoms and diatomic molecules in flow systems. The text also describes the production and detection of reactive species with lasers in static systems; the production of small positive ions in a mass spectrometer; and the discharge-excite

  16. Gas-Phase Growth of Heterostructures of Carbon Nanotubes and Bimetallic Nanowires

    Directory of Open Access Journals (Sweden)

    Whi Dong Kim

    2011-01-01

    Full Text Available A simple, inexpensive, and viable method for growing multiple heterostructured carbon nanotubes (CNTs over the entire surface of Ni-Al bimetallic nanowires (NWs in the gas phase was developed. Polymer-templated bimetallic nitrate NWs were produced by electrospinning in the first step, and subsequent calcination resulted in the formation of bimetallic oxide NWs by thermal decomposition. In the second step, free-floating bimetallic NWs were produced by spray pyrolysis in an environment containing hydrogen gas as a reducing gas. These NWs were continuously introduced into a thermal CVD reactor in order to grow CNTs in the gas phase. Scanning electron microscopy (SEM, transmission electron microscopy (TEM, and Raman spectrometry analyses revealed that the catalytic Ni sites exposed in the non-catalytic Al matrix over the entire surface of the bimetallic NWs were seeded to radially grow highly graphitized CNTs, which resembled “foxtail” structures. The grown CNTs were found to have a relatively uniform diameter of approximately 10±2 nm and 10 to 15 walls with a hollow core. The average length of the gas-phase-grown CNTs can be controlled between 100 and 1000 nm by adjusting the residence time of the free-floating bimetallic NWs in the thermal CVD reactor.

  17. Gas-phase SO2 in absorption towards massive protostars

    NARCIS (Netherlands)

    Keane, JV; Boonman, AMS; Tielens, AGGM; van Dishoeck, EF; Dishoeck, E. F.; Lahuis, F. van; Wright, C. M.; Doty, S. D.

    2001-01-01

    We present the first detection of the v(3) ro-vibrational band of gas-phase SO2 in absorption in the mid-infrared spectral region around 7.3 mum of a sample of deeply embedded massive protostars. Comparison with model spectra shows that the derived excitation temperatures correlate with previous C2H

  18. Unimolecular Gas-Phase Thermolysis of Ethyl Acetate

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Carlsen, Lars

    1983-01-01

    The unimolecular gas-phase thermolysis of ethyl acetate has been investigated by the Flash-Vacuum-Thermolysis/Field-Ionization Mass Spectrometry (FVT/FI-MS) method in combination with Collision Activation (CA) mass spectrometry at 1253K. Two predominant reactions are observed: elimination...

  19. Gas-Phase Thermolysis of a Thioketen-S-Oxide

    DEFF Research Database (Denmark)

    Carlsen, Lars; Egsgaard, Helge; Schaumann, Ernst

    1980-01-01

    The unimolecular gas-phase thermolytic decomposition of 1,1,3,3-tetramethyl-2-thiocarbonylcyclohexane S-oxide (3) has been studied as a function of temperature by a flash vacuum thermolysis (f.v.t.) technique. The products detected are the carbenes (4) and (5), the ketone (6), the keten (7), the ...

  20. SVOC partitioning between the gas phase and settled dust indoors

    DEFF Research Database (Denmark)

    Weschler, Charles J.; Nazaroff, W. W.

    2010-01-01

    Semivolatile organic compounds (SVOCs) are a major class of indoor pollutants. Understanding SVOC partitioning between the gas phase and settled dust is important for characterizing the fate of these species indoors and the pathways by which humans are exposed to them. Such knowledge also helps...

  1. The Dipeptide Ala-Gly in the Gas Phase

    Science.gov (United States)

    Bermúdez, Celina; Varela, Marcelino; Cabezas, Carlos; Peña, Isabel; Alonso, José L.

    2014-06-01

    The dipeptide Ala-Gly has been examined in gas phase by laser ablation molecular beam Fourier transform microwave (LA-MB-FTMW) spectroscopy in the frequency region 3-12 GHz. Three rotamers have been detected in the supersonic expansion. The quadrupole hyperfine structure of two 14N (I=1) nuclei has been totally resolved allowing the conclusive identification of one conformer.

  2. Experimental observables on nuclear liquid gas phase transition

    CERN Document Server

    Ma, Y G

    2006-01-01

    Progress on nuclear liquid gas phase transition (LGPT) or critical behavior has been simply reviewed and some signals of LGPT in heavy ion collisions, especially in NIMROD data, are focused. These signals include the power-law charge distribution, the largest fluctuation of the fragment observables, the nuclear Zipf law, caloric curve and critical exponent analysis etc.

  3. Gas-Phase IR Spectroscopy of Deprotonated Amino Acids

    NARCIS (Netherlands)

    Oomens, J.; Steill, J. D.; Redlich, B.

    2009-01-01

    Gas-phase infrared multiple photon dissociation (IRMPD) spectra have been recorded for the conjugate bases of a series of amino acids (Asp, Cys, Glu, Phe, Set, Trp, Tyr). The spectra are dominated by strong symmetric and antisymmetric carboxylate stretching modes around 1300 and 1600 cm(-1),

  4. Condensed phase decomposition and gas phase combustion of hydrazinium nitroformate

    NARCIS (Netherlands)

    Dragomir, O.E.; Tummers, M.J.; Veen, E.H. van; Heijden, A.E.D.M. van der; Roekaerts, D.J.E.M.

    2009-01-01

    This paper presents the results of a series of experiments on the condensed phase decomposition and the gas phase combustion of hydrazinium nitroformate (HNF). The experiments include SEM analysis of quenched samples that showed evidence of the formation of a foam layer. FTIR spectrometry and mass s

  5. Spectroscopic studies of cold, gas-phase biomolecular ions

    Science.gov (United States)

    Rizzo, Thomas R.; Stearns, Jaime A.; Boyarkin, Oleg V.

    While the marriage of mass spectrometry and laser spectroscopy is not new, developments over the last few years in this relationship have opened up new horizons for the spectroscopic study of biological molecules. The combination of electrospray ionisation for producing large biological molecules in the gas phase together with cooled ion traps and multiple-resonance laser schemes are allowing spectroscopic investigation of individual conformations of peptides with more than a dozen amino acids. Highly resolved infrared spectra of single conformations of such species provide important benchmarks for testing the accuracy of theoretical calculations. This review presents a number of techniques employed in our laboratory and in others for measuring the spectroscopy of cold, gas-phase protonated peptides. We show examples that demonstrate the power of these techniques and evaluate their extension to still larger biological molecules.

  6. Gas Phase Reactivity of Carboxylates with N-Hydroxysuccinimide Esters

    Science.gov (United States)

    Peng, Zhou; McGee, William M.; Bu, Jiexun; Barefoot, Nathan Z.; McLuckey, Scott A.

    2015-01-01

    N-hydroxysuccinimide (NHS) esters have been used for gas-phase conjugation reactions with peptides at nucleophilic sites, such as primary amines (N-terminus, ɛ-amine of lysine) or guanidines, by forming amide bonds through a nucleophilic attack on the carbonyl carbon. The carboxylate has recently been found to also be a reactive nucleophile capable of initiating a similar nucleophilic attack to form a labile anhydride bond. The fragile bond is easily cleaved, resulting in an oxygen transfer from the carboxylate-containing species to the reagent, nominally observed as a water transfer. This reactivity is shown for both peptides and non-peptidic species. Reagents isotopically labeled with O18 were used to confirm reactivity. This constitutes an example of distinct differences in reactivity of carboxylates between the gas phase, where they are shown to be reactive, and the solution phase, where they are not regarded as reactive with NHS esters.

  7. Gas-phase photocatalysis in μ-reactors

    DEFF Research Database (Denmark)

    Vesborg, Peter Christian Kjærgaard; Olsen, Jakob Lind; Henriksen, Toke Riishøj

    2010-01-01

    Gas-phase photocatalysis experiments may benefit from the high sensitivity and good time response in product detection offered by μ-reactors. We demonstrate this by carrying out CO oxidation and methanol oxidation over commercial TiO2 photocatalysts in our recently developed high-sensitivity reac......-sensitivity reactors. We demonstrate that the system exhibits great versatility in terms of photocatalyst, illumination source and target reaction.......Gas-phase photocatalysis experiments may benefit from the high sensitivity and good time response in product detection offered by μ-reactors. We demonstrate this by carrying out CO oxidation and methanol oxidation over commercial TiO2 photocatalysts in our recently developed high...

  8. Gas-Phase Photocatalytic Oxidation of Dimethylamine: The Reaction Pathway and Kinetics

    Directory of Open Access Journals (Sweden)

    Anna Kachina

    2007-01-01

    Full Text Available Gas-phase photocatalytic oxidation (PCO and thermal catalytic oxidation (TCO of dimethylamine (DMA on titanium dioxide was studied in a continuous flow simple tubular reactor. Volatile PCO products of DMA included ammonia, formamide, carbon dioxide, and water. Ammonia was further oxidized in minor amounts to nitrous oxide and nitrogen dioxide. Effective at 573 K, TCO resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide, and water. The PCO kinetic data fit well to the monomolecular Langmuir-Hinshelwood model, whereas TCO kinetic behaviour matched the first-order process. No deactivation of the photocatalyst during the multiple long-run experiments was observed.

  9. Substrate-free gas-phase synthesis of graphene sheets.

    Science.gov (United States)

    Dato, Albert; Radmilovic, Velimir; Lee, Zonghoon; Phillips, Jonathan; Frenklach, Michael

    2008-07-01

    We present a novel method for synthesizing graphene sheets in the gas phase using a substrate-free, atmospheric-pressure microwave plasma reactor. Graphene sheets were synthesized by passing liquid ethanol droplets into an argon plasma. The graphene sheets were characterized by transmission electron microscopy, electron energy loss spectroscopy, Raman spectroscopy, and electron diffraction. We prove that graphene can be created without three-dimensional materials or substrates and demonstrate a possible avenue to the large-scale synthesis of graphene.

  10. The Nucleoside Uridine Isolated in the Gas Phase**

    Science.gov (United States)

    Peña, Isabel; Cabezas, Carlos; Alonso, José L.

    2016-01-01

    Herein we present the first experimental observation of the isolated nucleoside uridine, placed in the gas phase by laser ablation and characterized by Fourier transform microwave techniques. Free from the bulk effects of their native environments, anti/C2’-endo-g+ conformation has been revealed as the most stable form of uridine. Intramolecular hydrogen bonds involving uracil and ribose moieties have been found to play an important role in the stabilization of the nucleoside. PMID:25683559

  11. Recent progress of nuclear liquid gas phase transition

    Institute of Scientific and Technical Information of China (English)

    MA Yu-Gang; SHEN Wen-Qing

    2004-01-01

    Recent progress on nuclear liquid gas phase transition (LGPT) has been reviewed, especially for the signals of LGPT in heavy ion collisions. These signals include the power-law charge distribution, cluster emission rate, nuclear Zipf law, bimodality, the largest fluctuation of the fragments, △ -scaling, caloric curve, phase coexistence diagram, critical temperature, critical exponent analysis, negative specific heat capacity and spinodal instability etc. The systematic works of the authors on experimental and theoretical LGPT are also introduced.

  12. Understanding Gas-Phase Ammonia Chemistry in Protoplanetary Disks

    Science.gov (United States)

    Chambers, Lauren; Oberg, Karin I.; Cleeves, Lauren Ilsedore

    2017-01-01

    Protoplanetary disks are dynamic regions of gas and dust around young stars, the remnants of star formation, that evolve and coagulate over millions of years in order to ultimately form planets. The chemical composition of protoplanetary disks is affected by both the chemical and physical conditions in which they develop, including the initial molecular abundances in the birth cloud, the spectrum and intensity of radiation from the host star and nearby systems, and mixing and turbulence within the disk. A more complete understanding of the chemical evolution of disks enables a more complete understanding of the chemical composition of planets that may form within them, and of their capability to support life. One element known to be essential for life on Earth is nitrogen, which often is present in the form of ammonia (NH3). Recent observations by Salinas et al. (2016) reveal a theoretical discrepancy in the gas-phase and ice-phase ammonia abundances in protoplanetary disks; while observations of comets and protostars estimate the ice-phase NH3/H2O ratio in disks to be 5%, Salinas reports a gas-phase NH3/H2O ratio of ~7-84% in the disk surrounding TW Hydra, a young nearby star. Through computational chemical modeling of the TW Hydra disk using a reaction network of over 5000 chemical reactions, I am investigating the possible sources of excess gas-phase NH3 by determining the primary reaction pathways of NH3 production; the downstream chemical effects of ionization by ultraviolet photons, X-rays, and cosmic rays; and the effects of altering the initial abundances of key molecules such as N and N2. Beyond providing a theoretical explanation for the NH3 ice/gas discrepancy, this new model may lead to fuller understanding of the gas-phase formation processes of all nitrogen hydrides (NHx), and thus fuller understanding of the nitrogen-bearing molecules that are fundamental for life as we know it.

  13. Optically-Based Diagnostics for Gas-Phase Laser Development

    Science.gov (United States)

    2010-08-01

    Phase Laser Development Acknowledgement of Support and Disclaimer This material is based upon work supported by Air Force Office of Scientific...00-2010 4. TITLE AND SUBTITLE Optically-Based Diagnostics for Gas-Phase Laser Development 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM...Sciences Inc. Role of Optical Diagnostics in High Energy Gas Laser Development  Chemically rich, energetic, reacting flow with competing phenomena

  14. Conformation of alkanes in the gas phase and pure liquids.

    Science.gov (United States)

    Thomas, Laura L; Christakis, Theodore J; Jorgensen, William L

    2006-10-26

    Monte Carlo (MC) statistical mechanics simulations have been carried out for the homologous alkane series of n-butane through n-dodecane in the gas phase and for the pure liquids at 298 K and 1 atm using the OPLS-AA force field. The study addresses potential cumulative deviations of computed properties and potential conformational differences between the gas phase and pure liquids, for example, from self-solvation in the gas phase. The average errors in comparison with experimental data for the computed densities and heats of vaporization are modest at 0.7% and 6.9%, respectively. Also, the invariant gas and liquid-phase results for average end-to-end distances and percentages of trans conformations for each nonterminal C-C bond assert that the conformer populations are not altered upon transfer from the gas phase to the pure liquid for the n-alkanes in this size range. Average end-to-end distances were also computed from the results of conformational searches and corroborated the MC findings. Quantitatively, the OPLS-AA result for the trans population of the C3-C4 bond in n-undecane is in close agreement with the findings from (13)C NMR experiments. Finally, previous work on determining the shortest n-alkane that does not have an all-trans global energy minimum has been extended. The smallest n-alkane with a hairpin geometry that is lower in energy than the all-trans conformer occurs for C(22)H(46) with OPLS-AA, though with a correction for GG sequences, the true turning point is likely in the C(16)-C(18) range.

  15. Gas phase chemical detection with an integrated chemical analysis system

    Energy Technology Data Exchange (ETDEWEB)

    CASALNUOVO,STEPHEN A.; FRYE-MASON,GREGORY CHARLES; KOTTENSTETTE,RICHARD; HELLER,EDWIN J.; MATZKE,CAROLYN M.; LEWIS,PATRICK R.; MANGINELL,RONALD P.; BACA,ALBERT G.; HIETALA,VINCENT M.

    2000-04-12

    Microfabrication technology has been applied to the development of a miniature, multi-channel gas phase chemical laboratory that provides fast response, small size, and enhanced versatility and chemical discrimination. Each analysis channel includes a sample preconcentrator followed by a gas chromatographic separator and a chemically selective surface acoustic wave detector array to achieve high sensitivity and selectivity. The performance of the components, individually and collectively, is described.

  16. Homogeneous gas phase models of relaxation kinetics in neon afterglow

    Directory of Open Access Journals (Sweden)

    Marković Vidosav Lj.

    2007-01-01

    Full Text Available The homogeneous gas phase models of relaxation kinetics (application of the gas phase effective coefficients to represent surface losses are applied for the study of charged and neutral active particles decay in neon afterglow. The experimental data obtained by the breakdown time delay measurements as a function of the relaxation time td (τ (memory curve is modeled in early, as well as in late afterglow. The number density decay of metastable states can explain neither the early, nor the late afterglow kinetics (memory effect, because their effective lifetimes are of the order of milliseconds and are determined by numerous collision quenching processes. The afterglow kinetics up to hundreds of milliseconds is dominated by the decay of molecular neon Ne2 + and nitrogen ions N2 + (present as impurities and the approximate value of N2 + ambipolar diffusion coefficient is determined. After the charged particle decay, the secondary emitted electrons from the surface catalyzed excitation of nitrogen atoms on the cathode determine the breakdown time delay down to the cosmic rays and natural radioactivity level. Due to the neglecting of number density spatial profiles, the homogeneous gas phase models give only the approximate values of the corresponding coefficients, but reproduce correctly other characteristics of afterglow kinetics from simple fits to the experimental data.

  17. Green synthesis of isopropyl myristate in novel single phase medium Part II: Packed bed reactor (PBR studies

    Directory of Open Access Journals (Sweden)

    Rajeshkumar N. Vadgama

    2015-12-01

    Full Text Available Isopropyl myristate is a useful functional molecule responding to the requirements of numerous fields of application in cosmetic, pharmaceutical and food industry. In the present work, lipase-catalyzed production of isopropyl myristate by esterification of myristic acid with isopropyl alcohol (molar ratio of 1:15 in the homogenous reaction medium was performed on a bench-scale packed bed reactors, in order to obtain suitable reaction performance data for upscaling. An immobilized lipase B from Candida antartica was used as the biocatalyst based on our previous study. The process intensification resulted in a clean and green synthesis process comprising a series of packed bed reactors of immobilized enzyme and water dehydrant. In addition, use of the single phase reaction system facilitates efficient recovery of the product with no effluent generated and recyclability of unreacted substrates. The single phase reaction system coupled with a continuous operating bioreactor ensures a stable operational life for the enzyme.

  18. Gas-Phase Covalent And Non-Covalent Ion/ion Chemistry Of Biological Macromolecules

    OpenAIRE

    Stutzman, John Robert

    2013-01-01

    Gas-phase ion/ion chemistry involves the interaction of oppositely charged ions inside of the mass spectrometer. During this gas-phase chemistry, particle transfer (i.e., proton and electron) or synthesis can occur at rapid reaction rates. Particle transfer represents a mature area of ion/ion chemistry, while selective covalent modification represents a fairly new area of gas-phase chemistry. Gas-phase covalent chemistry is based on traditional solution phase organic chemistry. The work de...

  19. A Simple and Rapid Method for Standard Preparation of Gas Phase Extract of Cigarette Smoke

    Science.gov (United States)

    Higashi, Tsunehito; Mai, Yosuke; Noya, Yoichi; Horinouchi, Takahiro; Terada, Koji; Hoshi, Akimasa; Nepal, Prabha; Harada, Takuya; Horiguchi, Mika; Hatate, Chizuru; Kuge, Yuji; Miwa, Soichi

    2014-01-01

    Cigarette smoke consists of tar and gas phase: the latter is toxicologically important because it can pass through lung alveolar epithelium to enter the circulation. Here we attempt to establish a standard method for preparation of gas phase extract of cigarette smoke (CSE). CSE was prepared by continuously sucking cigarette smoke through a Cambridge filter to remove tar, followed by bubbling it into phosphate-buffered saline (PBS). An increase in dry weight of the filter was defined as tar weight. Characteristically, concentrations of CSEs were represented as virtual tar concentrations, assuming that tar on the filter was dissolved in PBS. CSEs prepared from smaller numbers of cigarettes (original tar concentrations ≤15 mg/ml) showed similar concentration-response curves for cytotoxicity versus virtual tar concentrations, but with CSEs from larger numbers (tar ≥20 mg/ml), the curves were shifted rightward. Accordingly, the cytotoxic activity was detected in PBS of the second reservoir downstream of the first one with larger numbers of cigarettes. CSEs prepared from various cigarette brands showed comparable concentration-response curves for cytotoxicity. Two types of CSEs prepared by continuous and puff smoking protocols were similar regarding concentration-response curves for cytotoxicity, pharmacology of their cytotoxicity, and concentrations of cytotoxic compounds. These data show that concentrations of CSEs expressed by virtual tar concentrations can be a reference value to normalize their cytotoxicity, irrespective of numbers of combusted cigarettes, cigarette brands and smoking protocols, if original tar concentrations are ≤15 mg/ml. PMID:25229830

  20. Digluconate and Isopropyl Alcohol Biocide Formulation

    Directory of Open Access Journals (Sweden)

    Barbara Conway

    2012-10-01

    Full Text Available Effective surface disinfection is a fundamental infection control strategy within healthcare. This study assessed the antimicrobial efficacy of novel biocide formulations comprising 5% and 2% eucalyptus oil (EO combined with 2% chlorhexidine digluconate (CHG and 70% isopropyl alcohol (IPA contained within a wipe. The efficacy of this novel antimicrobial formulation to remove and eliminate methicillin-resistant Staphylococcus aureus (MRSA, Escherichia coli and Candida albicans from steel surfaces was investigated. Adpression studies of pre-contaminated wipes were also utilised to assess their potential to induce cross-contamination between hard surfaces. Furthermore, the bactericidal nature of the EO-formulation was established in addition to time-kill. The EO-containing formulations demonstrated bactericidal antimicrobial efficacy against all microorganisms and did not induce surface cross-contamination. There was no significant difference (p < 0.05 between the 5% and 2% EO formulations in their ability to remove microorganisms from steel surfaces, however both significantly (p < 0.05 removed more than the control formulations. Microbial biofilms were eliminated within 10 min (p < 0.05 when exposed to the EO formulations. Our novel EO-formulation demonstrated rapid antimicrobial efficacy for potential disinfection and elimination of microbial biofilms from hard surfaces and may therefore be a useful adjunct to current infection control strategies currently employed within healthcare facilities.

  1. Neurotransmitters in the Gas Phase: La-Mb Studies

    Science.gov (United States)

    Cabezas, C.; Mata, S.; López, J. C.; Alonso, J. L.

    2011-06-01

    LA-MB-FTMW spectroscopy combines laser ablation with Fourier transform microwave spectroscopy in supersonic jets overcoming the problems of thermal decomposition associated with conventional heating methods. We present here the results on LA-MB-FTMW studies of some neurotransmitters. Six conformers of dopamine, four of adrenaline, five of noradrenaline and three conformers of serotonin have been characterized in the gas phase. The rotational and nuclear quadrupole coupling constants extracted from the analysis of the rotational spectrum are directly compared with those predicted by ab initio methods to achieve the conclusive identification of different conformers and the experimental characterization of the intramolecular forces at play which control conformational preferences.

  2. Seven Conformers of Pipecolic Acid Identified in the Gas Phase

    Science.gov (United States)

    Cabezas, Carlos; Simao, Alcides; Alonso, José L.

    2016-06-01

    The multiconformational landscape of the non-proteinogenic cyclic amino acid pipecolic acid has been explored in the gas phase. Solid pipecolic acid (m.p. 280°C) was vaporized by laser ablation (LA) and expanded in a supersonic jet where the rotational spectra of seven conformers were obtained by broadband microwave spectroscopy (CP-FTMW). All conformers were conclusively identified by comparison of the experimental spectroscopic constants with those predicted theoretically. The relative stability of the conformers rests on a delicate balance of the different intramolecular hydrogen bonds established between the carboxylic and the amino groups.

  3. Gas-phase energetics of thorium fluorides and their ions.

    Science.gov (United States)

    Irikura, Karl K

    2013-02-14

    Gas-phase thermochemistry for neutral ThF(n) and cations ThF(n)(+) (n = 1-4) is obtained from large-basis CCSD(T) calculations, with a small-core pseudopotential on thorium. Electronic partition functions are computed with the help of relativistic MRCI calculations. Geometries, vibrational spectra, electronic fine structure, and ion appearance energies are tabulated. These results support the experimental results by Lau, Brittain, and Hildenbrand for the neutral species, except for ThF. The ion thermochemistry is presented here for the first time.

  4. Visible and Ultraviolet Spectroscopy of Gas Phase Rhodamine 575 Cations

    OpenAIRE

    Daly, Steven; Kulesza, Alexander; Knight, Geoffrey; Macaleese, Luke; Antoine, Rodolphe; Dugourd, Philippe

    2015-01-01

    International audience; The visible and ultraviolet spectroscopy of gas phase rhodamine 575 cations has been studied experimentally by action-spectroscopy in a modified linear ion trap between 220 and 590 nm and by time-dependent density functional theory (TDDFT) calculations. Three bands are observed that can be assigned to the electronic transitions S0 → S1, S0 → S3, and S0 → (S8,S9) according to the theoretical prediction. While the agreement between theory and experiment is excellent for ...

  5. The Influence of Mixing in High Temperature Gas Phase Reactions

    DEFF Research Database (Denmark)

    Østberg, Martin

    1996-01-01

    of NH3 by formation of NH2 and NH radicals.Mixing in reacting gas phase systems is described by an empirical mixing model (the droplet diffusion model). The mixing process is separated into macro- and micromixing. The macromixing is assumed to be ideal while the micromixing is modelled by molecular......The objective of this thesis is to describe the mixing in high temperature gas phase reactions.The Selective Non-Catalytic Reduction of NOx (referred as the SNR process) using NH3 as reductant was chosen as reaction system. This in-furnace denitrification process is made at around 1200 - 1300 K...... by injection of NH3 with carrier gas into the flue gas. NH3 can react with NO and form N2, but a competing reaction path is the oxidation of NH3 to NO.The SNR process is briefly described and it is shown by chemical kinetic modelling that OH radicals under the present conditions will initiate the reaction...

  6. Gas-Phase Acidities of Phosphorylated Amino Acids.

    Science.gov (United States)

    Stover, Michele L; Plummer, Chelsea E; Miller, Sean R; Cassady, Carolyn J; Dixon, David A

    2015-11-19

    Gas-phase acidities and heats of formation have been predicted at the G3(MP2)/SCRF-COSMO level of theory for 10 phosphorylated amino acids and their corresponding amides, including phospho-serine (pSer), -threonine (pThr), and -tyrosine (pTyr), providing the first reliable set of these values. The gas-phase acidities (GAs) of the three named phosphorylated amino acids and their amides have been determined using proton transfer reactions in a Fourier transform ion cyclotron mass spectrometer. Excellent agreement was found between the experimental and predicted GAs. The phosphate group is the deprotonation site for pSer and pThr and deprotonation from the carboxylic acid generated the lowest energy anion for pTyr. The infrared spectra were calculated for six low energy anions of pSer, pThr, and pTyr. For deprotonated pSer and pThr, good agreement is found between the experimental IRMPD spectra and the calculated spectra for our lowest energy anion structure. For pTyr, the IR spectra for a higher energy phosphate deprotonated structure is in good agreement with experiment. Additional experiments tested electrospray ionization (ESI) conditions for pTyr and determined that variations in solvent, temperature, and voltage can result in a different experimental GA value, indicating that ESI conditions affect the conformation of the pTyr anion.

  7. Star formation and gas phase history of the cosmic web

    Science.gov (United States)

    Snedden, Ali; Coughlin, Jared; Phillips, Lara Arielle; Mathews, Grant; Suh, In-Saeng

    2016-01-01

    We present a new method of tracking and characterizing the environment in which galaxies and their associated circumgalactic medium evolve. We have developed a structure finding algorithm that uses the rate of change of the density gradient to self-consistently parse and follow the evolution of groups/clusters, filaments and voids in large-scale structure simulations. We use this to trace the complete evolution of the baryons in the gas phase and the star formation history within each structure in our simulated volume. We vary the structure measure threshold to probe the complex inner structure of star-forming regions in poor clusters, filaments and voids. We find that the majority of star formation occurs in cold, condensed gas in filaments at intermediate redshifts (z ˜ 3). We also show that much of the star formation above a redshift z = 3 occurs in low-contrast regions of filaments, but as the density contrast increases at lower redshift, star formation switches to the high-contrast regions, or inner parts, of filaments. Since filaments bridge the void and cluster regions, it suggests that the majority of star formation occurs in galaxies in intermediate density regions prior to the accretion on to groups/clusters. We find that both filaments and poor clusters are multiphase environments distinguishing themselves by different distributions of gas phases.

  8. Nahoon: Time-dependent gas-phase chemical model

    Science.gov (United States)

    Wakelam, V.

    2014-09-01

    Nahoon is a gas-phase chemical model that computes the chemical evolution in a 1D temperature and density structure. It uses chemical networks downloaded from the KInetic Database for Astrochemistry (KIDA) but the model can be adapted to any network. The program is written in Fortran 90 and uses the DLSODES (double precision) solver from the ODEPACK package to solve the coupled stiff differential equations. The solver computes the chemical evolution of gas-phase species at a fixed temperature and density and can be used in one dimension (1D) if a grid of temperature, density, and visual extinction is provided. Grains, both neutral and negatively charged, and electrons are considered as chemical species and their concentrations are computed at the same time as those of the other species. Nahoon contains a test to check the temperature range of the validity of the rate coefficients and avoid extrapolations outside this range. A test is also included to check for duplication of chemical reactions, defined over complementary ranges of temperature.

  9. Optical Absorptions of Oxygenated Carbon Chain Cations in the Gas Phase

    Science.gov (United States)

    Hardy, F.-X.; Rice, C. A.; Chakraborty, A.; Fulara, J.; Maier, J. P.

    2016-06-01

    The gas-phase electronic spectra of linear OC4O+ and a planar C6H2O+ isomer were obtained at a rotational temperature of ≈10 K. Absorption measurements in a 6 K neon matrix were followed by gas-phase observations in a cryogenic radiofrequency ion trap. The origin bands of the 1{}2{{{\\Pi }}}u ≤ftarrow X{}2{{{\\Pi }}}g transition of OC4O+ and the 1{}2A{}2 ≤ftarrow X{}2B1 of HCCC(CO)CCH+ lie at 417.31 ± 0.01 nm and 523.49 ± 0.01 nm, respectively. These constitute the first electronic spectra of oxygenated carbon chain cations studied under conditions that are relevant to the diffuse interstellar bands (DIBs), as both have a visible transition. The recent analysis of the 579.5 nm DIB indicates that small carriers, five to seven heavy atoms, continue to be possible candidates (Huang & Oka 2015). Astronomical implications are discussed regarding this kind of oxygenated molecules.

  10. The α-Effect and Competing Mechanisms: The Gas-Phase Reactions of Microsolvated Anions with Methyl Formate

    Science.gov (United States)

    Thomsen, Ditte L.; Nichols, Charles M.; Reece, Jennifer N.; Hammerum, Steen; Bierbaum, Veronica M.

    2013-12-01

    The enhanced reactivity of α-nucleophiles, which contain an electron lone pair adjacent to the reactive site, has been demonstrated in solution and in the gas phase and, recently, for the gas-phase SN2 reactions of the microsolvated HOO-(H2O) ion with methyl chloride. In the present work, we continue to explore the significance of microsolvation on the α-effect as we compare the gas-phase reactivity of the microsolvated α-nucleophile HOO-(H2O) with that of microsolvated normal alkoxy nucleophiles, RO-(H2O), in reactions with methyl formate, where three competing reactions are possible. The results reveal enhanced reactivity of HOO-(H2O) towards methyl formate, and clearly demonstrate the presence of an overall α-effect for the reactions of the microsolvated α-nucleophile. The association of the nucleophiles with a single water molecule significantly lowers the degree of proton abstraction and increases the SN2 and BAC2 reactivity compared with the unsolvated analogs. HOO-(H2O) reacts with methyl formate exclusively via the BAC2 channel. While microsolvation lowers the overall reaction efficiency, it enhances the BAC2 reaction efficiency for all anions compared with the unsolvated analogs. This may be explained by participation of the solvent water molecule in the BAC2 reaction in a way that continuously stabilizes the negative charge throughout the reaction.

  11. Conformational Study of Taurine in the Gas Phase

    Science.gov (United States)

    Cortijo, Vanessa; Sanz, M. Eugenia; López, Juan C.; Alonso, José L.

    2009-08-01

    The conformational preferences of the amino sulfonic acid taurine (NH2-CH2-CH2-SO3H) have been investigated in the gas phase by laser ablation molecular beam Fourier transform microwave spectroscopy (LA-MB-FTMW) in the 6-14 GHz frequency range. One conformer has been observed, and its rotational, centrifugal distortion, and hyperfine quadrupole coupling constants have been determined from the analysis of its rotational spectrum. Comparison of the experimental constants with those calculated theoretically identifies the detected conformer unambiguously. The observed conformer of taurine is stabilized by an intramolecular hydrogen bond O-H···N between the hydrogen of the sulfonic acid group and the nitrogen atom of the amino group.

  12. Silicon Nanowire‐Based Devices for Gas-Phase Sensing

    Directory of Open Access Journals (Sweden)

    Anping Cao

    2013-12-01

    Full Text Available Since their introduction in 2001, SiNW-based sensor devices have attracted considerable interest as a general platform for ultra-sensitive, electrical detection of biological and chemical species. Most studies focus on detecting, sensing and monitoring analytes in aqueous solution, but the number of studies on sensing gases and vapors using SiNW-based devices is increasing. This review gives an overview of selected research papers related to the application of electrical SiNW-based devices in the gas phase that have been reported over the past 10 years. Special attention is given to surface modification strategies and the sensing principles involved. In addition, future steps and technological challenges in this field are addressed.

  13. Theory of Gas Phase Scattering and Reactivity for Astrochemistry

    CERN Document Server

    Wiesenfeld, Laurent; Caselli, Paola; Faure, Alexandre; Bizzocchi, Luca; Brandão, João; Duflot, Denis; Herbst, Eric; Klippenstein, Stephen J; Komatsuzaki, Tamiki; Puzzarini, Cristina; Roncero, Octavio; Teramoto, Hiroshi; Toda, Mikito; van der Avoird, Ad; Waalkens, Holger

    2016-01-01

    Because of the very peculiar conditions of chemistry in many astrophysical gases (low densities, mostly low temperatures, kinetics-dominated chemical evolution), great efforts have been devoted to study molecular signatures and chemical evolution. While experiments are being performed in many laboratories, it appears that the efforts directed towards theoretical works are not as strong. This report deals with the present status of chemical physics/physical chemistry theory, for the qualitative and quantitative understanding of kinetics of molecular scattering, being it reactive or inelastic. By gathering several types of expertise, from applied mathematics to physical chemistry, dialog is made possible, as a step towards new and more adapted theoretical frameworks, capable of meeting the theoretical, methodological and numerical challenges of kinetics-dominated gas phase chemistry in astrophysical environments. A state of the art panorama is presented, alongside present-day strengths and shortcomings. However...

  14. Synthesis and Gas Phase Thermochemistry of Germanium-Containing Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Classen, Nathan Robert [Iowa State Univ., Ames, IA (United States)

    2002-01-01

    The driving force behind much of the work in this dissertation was to gain further understanding of the unique olefin to carbene isomerization observed in the thermolysis of 1,1-dimethyl-2-methylenesilacyclobutane by finding new examples of it in other silicon and germanium compounds. This lead to the examination of a novel phenylmethylenesilacyclobut-2-ene, which did not undergo olefin to carbene rearrangement. A synthetic route to methylenegermacyclobutanes was developed, but the methylenegermacyclobutane system exhibited kinetic instability, making the study of the system difficult. In any case the germanium system decomposed through a complex mechanism which may not include olefin to carbene isomerization. However, this work lead to the study of the gas phase thermochemistry of a series of dialkylgermylene precursors in order to better understand the mechanism of the thermal decomposition of dialkylgermylenes. The resulting dialkylgermylenes were found to undergo a reversible intramolecular β C-H insertion mechanism.

  15. Statistical Physics of Nanoparticles in the Gas Phase

    CERN Document Server

    Hansen, Klavs

    2013-01-01

    Thermal processes are ubiquitous and an understanding of thermal phenomena is essential for a complete description of the physics of nanoparticles, both for the purpose of modeling the dynamics of the particles and for the correct interpretation of experimental data. This book has the twofold aim to present coherently the relevant results coming from the recent scientific literature and to guide the readers through the process of deriving results, enabling them to explore the limits of the mathematical approximations and test the power of the method. The book is focused on the fundamental properties of nanosystems in the gas phase. For this reason there is a strong emphasis on microcanonical physics. Each chapter is enriched with exercises and 3 Appendices provide additional useful materials.

  16. Enhancement of gas phase heat transfer by acoustic field application.

    Science.gov (United States)

    Komarov, Sergey; Hirasawa, Masahiro

    2003-06-01

    This study discusses a possibility for enhancement of heat transfer between solids and ambient gas by application of powerful acoustic fields. Experiments are carried out by using preheated Pt wires (length 0.1-0.15 m, diameter 50 and 100 micro m) positioned at the velocity antinode of a standing wave (frequency range 216-1031 Hz) or in the path of a travelling wave (frequency range 6.9-17.2 kHz). A number of experiments were conducted under conditions of gas flowing across the wire surface. Effects of sound frequency, sound strength, gas flow velocity and wire preheating temperature on the Nusselt number are examined with and without sound application. The gas phase heat transfer rate is enhanced with acoustic field strength. Higher temperatures result in a vigorous radiation from the wire surface and attenuate the effect of sound. The larger the gas flow velocity, the smaller is the effect of sound wave on heat transfer enhancement.

  17. Visible and ultraviolet spectroscopy of gas phase protein ions.

    Science.gov (United States)

    Antoine, Rodolphe; Dugourd, Philippe

    2011-10-06

    Optical spectroscopy has contributed enormously to our knowledge of the structure and dynamics of atoms and molecules and is now emerging as a cornerstone of the gas phase methods available for investigating biomolecular ions. This article focuses on the UV and visible spectroscopy of peptide and protein ions stored in ion traps, with emphasis placed on recent results obtained on protein polyanions, by electron photodetachment experiments. We show that among a large number of possible de-excitation pathways, the relaxation of biomolecular polyanions is mainly achieved by electron emission following photo-excitation in electronically excited states. Electron photodetachment is a fast process that occurs prior to relaxation on vibrational degrees of freedom. Electron photodetachment yield can then be used to record gas phase action spectra for systems as large as entire proteins, without the limitation of system size that would arise from energy redistribution on numerous modes and prevent fragmentation after the absorption of a photon. The optical activity of proteins in the near UV is directly related to the electronic structure and optical absorption of aromatic amino acids (Trp, Phe and Tyr). UV spectra for peptides and proteins containing neutral, deprotonated and radical aromatic amino acids were recorded. They displayed strong bathochromic shifts. In particular, the results outline the privileged role played by open shell ions in molecular spectroscopy which, in the case of biomolecules, is directly related to their reactivity and biological functions. The optical shifts observed are sufficient to provide unambiguous fingerprints of the electronic structure of chromophores without the requirement of theoretical calculations. They constitute benchmarks for calculating the absorption spectra of chromophores embedded in entire proteins and could be used in the future to study biochemical processes in the gas phase involving charge transfer in aromatic amino acids

  18. Synthesis and Gas Phase Thermochemistry of Germanium-Containing Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Nathan Robert Classen

    2002-12-31

    The driving force behind much of the work in this dissertation was to gain further understanding of the unique olefin to carbene isomerization observed in the thermolysis of 1,1-dimethyl-2-methylenesilacyclobutane by finding new examples of it in other silicon and germanium compounds. This lead to the examination of a novel phenylmethylenesilacyclobut-2-ene, which did not undergo olefin to carbene rearrangement. A synthetic route to methylenegermacyclobutanes was developed, but the methylenegermacyclobutane system exhibited kinetic instability, making the study of the system difficult. In any case the germanium system decomposed through a complex mechanism which may not include olefin to carbene isomerization. However, this work lead to the study of the gas phase thermochemistry of a series of dialkylgermylene precursors in order to better understand the mechanism of the thermal decomposition of dialkylgermylenes. The resulting dialkylgermylenes were found to undergo a reversible intramolecular {beta} C-H insertion mechanism.

  19. Ceramic microreactors for heterogeneously catalysed gas-phase reactions.

    Science.gov (United States)

    Knitter, Regina; Liauw, Marcel A

    2004-08-01

    The high surface to volume ratio of microchannel components offers many advantages in micro chemical engineering. It is obvious, however, that the reactor material and corrosion phenomena play an important role when applying these components. For chemical reactions at very high temperatures or/and with corrosive reactants involved, microchannel components made of metals or polymers are not suited. Hence, a modular microreactor system made of alumina was developed and fabricated using a rapid prototyping process chain. With exchangeable inserts the system can be adapted to the requirements of various reactions. Two heterogeneously catalysed gas-phase reactions (oxidative coupling of methane, isoprene selective oxidation to citraconic anhydride) were investigated to check the suitability of the system at temperatures of up to 1000 degrees C. Apart from the high thermal and chemical resistance, the lack of any blind activity was found to be another advantage of ceramic components.

  20. Molecular ions of ionic liquids in the gas phase.

    Science.gov (United States)

    Gross, Jürgen H

    2008-09-01

    Ionic liquids form neutral ion pairs (CA) upon evaporation. The softness of the gas-phase ionization of field ionization has been used to generate "molecular ions," CA(+*), of ionic liquids, most probably by neutralization of the anion. In detail, 1-ethyl-3-methylimidazolium-thiocyanate, [C(6)H(11)N(2)](+) [SCN](-), 1-butyl-3-methylimidazolium-tricyanomethide, [C(8)H(15)N(2)](+) [C(4)N(3)](-), N-butyl-3-methylpyridinium-dicyanamide, [C(10)H(16)N](+) [C(2)N(3)](-), and 1-butyl-1-methylpyrrolidinium-bis[(trifluormethyl)sulfonyl]amide, [C(9)H(20)N](+) [C(2)F(6)NO(4)S(2)](-) were used. The assignment as CA(+*) ions, which has been confirmed by accurate mass measurements and misassignments due to thermal decomposition of the ionic liquids, has been ruled out by field desorption and electrospray ionization mass spectrometry of the residues.

  1. Gas-phase synthesis of magnetic metal/polymer nanocomposites.

    Science.gov (United States)

    Starsich, Fabian H L; Hirt, Ann M; Stark, Wendelin J; Grass, Robert N

    2014-12-19

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

  2. Gas-phase synthesis of magnetic metal/polymer nanocomposites

    Science.gov (United States)

    Starsich, Fabian H. L.; Hirt, Ann M.; Stark, Wendelin J.; Grass, Robert N.

    2014-12-01

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

  3. Weak intermolecular interactions in gas-phase NMR

    CERN Document Server

    Garbacz, Piotr; Jackowski, Karol; Moszynski, Robert; Jaszunski, Michal

    2011-01-01

    Gas-phase NMR spectra demonstrating the effect of weak intermolecular forces on the NMR shielding constants of the interacting species are reported. We analyse the interaction of the molecular hydrogen isotopomers with He, Ne, and Ar, and the interaction in the He-CO_2 dimer. The same effects are studied for all these systems in the ab initio calculations. The comparison of the experimental and computed shielding constants is shown to depend strongly on the treatment of the bulk susceptibility effects, which determine in practice the pressure dependence of the experimental values. Best agreement of the results is obtained when the bulk susceptibility correction in rare gas solvents is evaluated from the analysis of the He-rare gas interactions, and when the shielding of deuterium in D_2-rare gas systems is considered.

  4. Gas-phase spectroscopy of ferric heme-NO complexes

    DEFF Research Database (Denmark)

    Wyer, J.A.; Jørgensen, Anders; Pedersen, Bjarke

    2013-01-01

    Weakly bound complexes between ferric heme cations and NO were synthesised in the gas phase from ion-molecule reactions, and their absorption measured based on photodissociation yields. The Soret band, which serves as an important marker band for heme-protein spectroscopy, is maximal at 357±5 nm...... and significantly blue-shifted compared to ferric heme nitrosyl proteins (maxima between 408 and 422 nm). This is in stark contrast to the Q-band absorption where the protein microenvironment is nearly innocent in perturbing the electronic structure of the porphyrin macrocycle. Photodissociation is primarily...... in vacuo and to ferric heme proteins, demonstrating the perturbing effect of the protein environment or the axial amino acid ligand, in contrast to Q-band absorption, where the environment is nearly innocent....

  5. Alkylation of toluene with isopropyl alcohol over SAPO-5 catalyst

    Indian Academy of Sciences (India)

    Sreedevi Upadhyayula

    2009-03-01

    Isopropylation of toluene with isopropyl alcohol was studied over the large pore silicon alumino phosphate molecular sieves (SAPO-5) with varying Si content. Toluene conversion was found to increase with increase in the Si of the catalysts. The effect of temperature on yields of cymene was studied in the range of 453 to 553 K. The highest yield and selectivity for cymene was observed at 513 K. Good cymene selectivity was confirmed with the absence of -propyl toluene in the product. The catalyst activity, in terms of -cymene selectivity, remained almost stable during a nine hour time on stream run. Enhanced cymene selectivity and decreased -cymene selectivity was observed with increase in the toluene to isopropyl alcohol feed mole ratio from 2 to 8. Power law model and L-H-H-W model fitted the experimental data well and are used to explain the kinetics of this reaction.

  6. The Northwest Infrared (NWIR) gas-phase spectral database of industrial and environmental chemicals: Recent updates

    Energy Technology Data Exchange (ETDEWEB)

    Brauer, Carolyn S.; Johnson, Timothy J.; Blake, Thomas A.; Sharpe, Steven W.; Sams, Robert L.; Tonkyn, Russell G.

    2014-05-22

    With continuing improvements in both standoff- and point-sensing techniques, there is an ongoing need for high-quality infrared spectral databases. The Northwest Infrared Database (NWIR) contains quantitative, gas-phase infrared spectra of nearly 500 pure chemical species that can be used for a variety of applications such as atmospheric monitoring, biomass burning studies, etc. The data, recorded at 0.1 cm-1 resolution, are pressure broadened to one atmosphere (N2) in order to mimic atmospheric conditions. Each spectrum is a composite composed of multiple individual measurements. Recent updates to the database include over 60 molecules that are known or suspected biomass-burning effluents. Examples from this set of measurements will be presented and experimental details will be discussed in the context of the utility of NWIR for environmental applications.

  7. Synthesis of carbon nanotubes by plasma-enhanced CVD process: gas phase study of synthesis conditions

    OpenAIRE

    Guláš, Michal; Cojocaru, Costel Sorin; Fleaca, Claudiu; Farhat, Samir; Veis, Pavel; Le Normand, Francois

    2008-01-01

    International audience; To support experimental investigations, a model based on ChemkinTM software was used to simulate gas phase and surface chemistry during plasma-enhanced catalytic CVD of carbon nanotubes. According to these calculations, gas phase composition, etching process and growth rates are calculated. The role of several carbon species, hydrocarbon molecules and ions in the growth mechanism of carbon nanotubes is presented in this study. Study of different conditions of gas phase ...

  8. Synthesis of carbon nanbotubes by plasma-enhanced CVD process: gas phase study of synthesis conditions

    Science.gov (United States)

    Guláš, M.; Cojocaru, C. S.; Fleaca, C. T.; Farhat, S.; Veis, P.; Le Normand, F.

    2008-09-01

    To support experimental investigations, a model based on Chemkin^TM software was used to simulate gas phase and surface chemistry during plasma-enhanced catalytic CVD of carbon nanotubes. According to these calculations, gas phase composition, etching process and growth rates are calculated. The role of several carbon species, hydrocarbon molecules and ions in the growth mechanism of carbon nanotubes is presented in this study. Study of different conditions of gas phase activation sources and pressure is performed.

  9. Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities

    Directory of Open Access Journals (Sweden)

    R. E. Dunmore

    2015-09-01

    Full Text Available Hydrocarbons are key precursors to two priority air pollutants, ozone and particulate matter. Those with two to seven carbons have historically been straightforward to observe and have been successfully reduced in many developed cities through air quality policy interventions. Longer chain hydrocarbons released from diesel vehicles are not considered explicitly as part of air quality strategies and there are few direct measurements of their gaseous abundance in the atmosphere. This study describes the chemically comprehensive and continuous measurements of organic compounds in a developed megacity (London, which demonstrate that on a seasonal median basis, diesel-related hydrocarbons represent only 20–30 % of the total hydrocarbon mixing ratio but comprise more than 50 % of the atmospheric hydrocarbon mass and are a dominant local source of secondary organic aerosols. This study shows for the first time that 60 % of the winter primary hydrocarbon hydroxyl radical reactivity is from diesel-related hydrocarbons and using the maximum incremental reactivity scale, we predict that they contribute up to 50 % of the ozone production potential in London. Comparing real-world urban composition with regulatory emissions inventories in the UK and US highlights a previously unaccounted for, but very significant, under-reporting of diesel-related hydrocarbons; an underestimation of a factor ~4 for C9 species rising to a factor of over 70 for C12 during winter. These observations show that hydrocarbons from diesel vehicles can dominate gas phase reactive carbon in cities with high diesel fleet fractions. Future control of urban particulate matter and ozone in such locations requires a shift in policy focus onto gas phase hydrocarbons released from diesels as this vehicle type continues to displace gasoline world-wide.

  10. A Standardized Method for the Preparation of a Gas Phase Extract of Cigarette Smoke.

    Science.gov (United States)

    Higashi, Tsunehito; Mai, Yosuke; Mazaki, Yuichi; Horinouchi, Takahiro; Miwa, Soichi

    2016-01-01

    The gas phase of cigarette smoke is important from the viewpoint of human health, because it can pass through alveolar epithelium and enter the circulation. There is no standard method for the preparation of a gas phase extract of cigarette smoke (CSE), although CSE is widely used for research instead of whole cigarette smoke. We have established a standard method for the preparation of CSE. One cigarette per trial is continuously combusted under a reduced pressure generated by an aspiration pump with a velocity of 1.050 L/min: the main stream of the smoke is passed through a Cambridge filter to remove tar, and subsequently, bubbled through a glass ball filter (pore size, 20-30 µm) into 15 mL of phosphate-buffered saline (PBS). To express the concentration of CSE, a virtual tar concentration is introduced, which is calculated assuming that tar trapped on the Cambridge filter is dissolved in the PBS. CSEs prepared from smaller numbers of cigarettes (original virtual tar concentration≤15 mg/mL) show similar concentration-response curves for cytotoxicity versus virtual tar concentrations. CSEs prepared from various brands of cigarettes and by different smoking regimes (continuous and puff smoking) show similar cytotoxic potency if the virtual tar concentrations are the same. In conclusion, using the standardized method for CSE preparation in combination with the virtual tar concentration, it becomes possible to simply and rapidly prepare standard CSEs with defined concentrations from any brand of cigarettes, which are toxicologically equivalent to CSE prepared by puff smoking.

  11. Characterization of a pilot plant airlift tower loop bioreactor: II. Evaluation of global mixing properties of the gas phase during yeast cultivation.

    Science.gov (United States)

    Fröhlich, S; Lotz, M; Korte, T; Lübbert, A; Schügerl, K; Seekamp, M

    1991-04-25

    Saccharomyces cerevisiae was cultivated in a 4-m(3) pilot plant airlift tower loop reactor with a draft tube in batch and continuous operations and for comparison in a laboratory airlift tower loop reactor of 0.08 m(3) volume. The reactors were characterized during and after the cultivation by measuring the distributions of the residence times of the gas phase with pseudostochastic tracer signals and mass spectrometer and by evaluating the mixing in the liquid phase with a pulse-shaped volatile tracer signal and mass spectrometer as a detector. The mean residence times and the intensities of the axial mixing in the riser and downcomer, the circulation times of the gas phase, and the fraction of the recirculated gas phase were evaluated and compared.

  12. The gas-phase ozonolysis of α-humulene.

    Science.gov (United States)

    Beck, M; Winterhalter, R; Herrmann, F; Moortgat, G K

    2011-06-21

    α-Humulene contains three double bonds (DB), and after ozonolysis of the first DB the first-generation products are still reactive towards O(3) and produce second- and third-generation products. The primary aim of this study consisted of identifying the products of the three generations, focusing on the carboxylic acids, which are known to have a high aerosol formation potential. The experiments were performed in a 570 litre spherical glass reactor at 295 K and 730 Torr. Initial mixing ratios were 260-2090 ppb for O(3) and 250-600 ppb for α-humulene in synthetic air. Reactants and gas-phase products were measured by in situ FTIR spectroscopy. Particulate products were sampled on Teflon filters, extracted with methanol and analyzed by LC-MS/MS-TOF. Using cyclohexane (10-100 ppm) as an OH-radical scavenger and by monitoring the yield of cyclohexanone by PTR-MS, an OH-yield of (10.5 ± 0.7)% was determined for the ozonolysis of the first DB, and (12.9 ± 0.7)% of the first-generation products. The rate constant of the reaction of O(3) with α-humulene is known as k(0) = 1.17 × 10(-14) cm(3) molecule(-1) s(-1) [Y. Shu and R. Atkinson, Int. J. Chem. Kinet., 1994, 26, 1193-1205]. The reaction rate constants of O(3) with the first-generation products and the second-generation products were, respectively, determined as k(1) = (3.6 ± 0.9) × 10(-16) and k(2) = (3.0 ± 0.7) × 10(-17) cm(3) molecule(-1) s(-1) by Facsimile-simulation of the observed ozone decay by FTIR. A total of 37 compounds in the aerosol phase and 5 products in the gas phase were tentatively identified: 25 compounds of the first-generation products contained C13-C15 species, 9 compounds of the second-generation products contained C8-C11 species, whereas 8 compounds of the third-generation products contained C4-C6 species. The products of all three generations consisted of a variety of dicarboxylic-, hydroxy-oxocarboxylic- and oxo-carboxylic acids. The formation mechanisms of some of the products are

  13. Gas-phase synthesis of semiconductor nanocrystals and its applications

    Science.gov (United States)

    Mandal, Rajib

    Luminescent nanomaterials is a newly emerging field that provides challenges not only to fundamental research but also to innovative technology in several areas such as electronics, photonics, nanotechnology, display, lighting, biomedical engineering and environmental control. These nanomaterials come in various forms, shapes and comprises of semiconductors, metals, oxides, and inorganic and organic polymers. Most importantly, these luminescent nanomaterials can have different properties owing to their size as compared to their bulk counterparts. Here we describe the use of plasmas in synthesis, modification, and deposition of semiconductor nanomaterials for luminescence applications. Nanocrystalline silicon is widely known as an efficient and tunable optical emitter and is attracting great interest for applications in several areas. To date, however, luminescent silicon nanocrystals (NCs) have been used exclusively in traditional rigid devices. For the field to advance towards new and versatile applications for nanocrystal-based devices, there is a need to investigate whether these NCs can be used in flexible and stretchable devices. We show how the optical and structural/morphological properties of plasma-synthesized silicon nanocrystals (Si NCs) change when they are deposited on stretchable substrates made of polydimethylsiloxane (PDMS). Synthesis of these NCs was performed in a nonthermal, low-pressure gas phase plasma reactor. To our knowledge, this is the first demonstration of direct deposition of NCs onto stretchable substrates. Additionally, in order to prevent oxidation and enhance the luminescence properties, a silicon nitride shell was grown around Si NCs. We have demonstrated surface nitridation of Si NCs in a single step process using non?thermal plasma in several schemes including a novel dual-plasma synthesis/shell growth process. These coated NCs exhibit SiNx shells with composition depending on process parameters. While measurements including

  14. Gas-phase products and secondary organic aerosol formation from the ozonolysis and photooxidation of myrcene

    Science.gov (United States)

    Böge, Olaf; Mutzel, Anke; Iinuma, Yoshiteru; Yli-Pirilä, Pasi; Kahnt, Ariane; Joutsensaari, Jorma; Herrmann, Hartmut

    2013-04-01

    Terrestrial vegetation releases a great variety of volatile organic compounds (VOC) into the atmosphere. Monoterpenes, like myrcene, contribute significantly to this global biogenic VOC emission. In the atmosphere, monoterpenes rapidly undergo oxidation reactions by OH radicals (mainly during the daytime), NO3 radicals (mainly during the nighttime) and O3 to form multifunctional oxidation products. The products of these reactions are likely to be of low volatility and hence might lead to secondary organic aerosol (SOA) formation. In the present study, we report results from a series of chamber experiments performed in the LEAK chamber at TROPOS in which the gas-phase products and SOA yields obtained from myrcene O3 reactions with and without an OH radical scavenger as well as from the myrcene OH radical reaction in the presence of NOx have been measured. During the experiments the consumption of myrcene as well as the formation of gas-phase products was monitored using a proton transfer reaction mass spectrometer (PTR-MS). Ozone concentration was measured by an O3 monitor and the mixing ratios of nitrogen oxides were measured by a NOx monitor. Particle size distributions between 3-900 nm were monitored every 11 min using a differential mobility particle sizer (DMPS) system. In addition to the products observed by means of the PTR-MS by their m/z values, an identification of carbonylic compounds by their DNPH derivatives was performed. Beside low molecular mass products the formation of 4-vinyl-4-pentenal with a yield of 55 % in myrcene ozonolysis has been observed. The further oxidation of this major first generation product lead to the formation of two dicarbonylic products with m/z 113 and to SOA formation. The influence of the continuing oxidation of 4-vinyl-4-pentenal on SOA formation will be discussed in detail. The emergence of the gas-phase product hydroxyacetone as direct result of the myrcene ozone reaction will be mooted, because hydroxyacetone seems to

  15. CHAOS II: Gas-Phase Abundances in NGC 5194

    CERN Document Server

    Croxall, Kevin V; Berg, Danielle; Skillman, Evan D; Moustakas, John

    2015-01-01

    We have observed NGC5194 (M51a) as part of the CHemical Abundances of Spirals (CHAOS) project. Using the Multi Object Double Spectrographs (MODS) on the Large Binocular Telescope (LBT) we are able to measure one or more of the temperature-sensitive auroral lines ([O III] 4363, [N II] 5755, [S III] 6312) and thus measure "direct" gas-phase abundances in 29 individual HII regions. [O III] 4363 is only detected in two HII regions both of which show indications of excitation by shocks. We compare our data to previous direct abundances measured in NGC5194 and find excellent agreement for all but one region (Delta[log(O/H)] ~ 0.04). We find no evidence of trends in Ar/O, Ne/O, or S/O within NGC5194 or compared to other galaxies. We find modest negative gradients in both O/H and N/O with very little scatter (sigma = -0.62) suggests secondary nitrogen production is responsible for a significantly larger fraction of nitrogen (e.g., factor of 8-10) relative to primary production mechanisms than predicted by theoretica...

  16. Gas Phase Conformations of Tetrapeptide Glycine-Phenylalanine-Glycine-Glycine

    Institute of Scientific and Technical Information of China (English)

    Hui-bin Chen; Yao Wang; Xin Chen; Zi-jing Lin

    2012-01-01

    Systematic search of the potential energy surface of tetrapeptide glycine-phenylalanineglycine-glycine (GFGG) in gas phase is conducted by a combination of PM3,HF and BHandHLYP methods.The conformational search method is described in detail.The relative electronic energies,zero point vibrational energies,dipole moments,rotational constants,vertical ionization energies and the temperature.dependent conformational distributions for a number of important conformers are obtained.The structural characteristics of these conformers are analyzed and it is found that the entropic effect is a dominating factor in determining the relative stabilities of the conformers.The measurements of dipole moments and some characteristic IR mode are shown to be effective approaches to verify the theoretical prediction.The structures of the low energy GFGG conformers are also analyzed in their connection with the secondary structures of proteins.Similarity between the local structures of low energy GFGG conformers and the α-helix is discussed and manyβ- and γ-turn local structures in GFGG conformers are found.

  17. Reactions of molecular dications in the gas phase

    CERN Document Server

    Tafadar, N N

    2001-01-01

    This thesis presents the results from a series of experiments investigating the reactivity of gas phase molecular dications with neutral collision partners, at collision energies between 3 and 13 eV in the laboratory frame using a crossed-beam apparatus. The experiments involve measurement of product ion intensities, which are determined by means of time of flight mass spectrometry. The experimental methodology, together with relevant theory is described in the thesis. The relative intensities of product ions formed are a powerful probe of the reaction mechanism. Where appropriate, the reactions are examined for isotope effects by using the isotopic analogue of the neutral collision partner. Our investigation of the CF sub 3 sup 2 sup + /Ar collision system shows neutral loss and electron transfer dominating the product ion yield. The variation of the neutral loss ion yield with collision energy provides a first estimate of the bond energy of the weak CF sub 2 sup 2 sup + -F bond. Ab initio calculations indic...

  18. Condensation of Cu nanoparticles from the gas phase

    Science.gov (United States)

    Chepkasov, I. V.; Gafner, Yu. Ya.; Gafner, S. L.; Bardahanov, S. P.

    2016-10-01

    In order to determine the most efficient modes of copper-nanoparticle synthesis, a number of experiments on evaporation with the subsequent condensation of the initial material in the argon atmosphere have been carried out. In the course of the experiments, it has been discovered that intensified evaporation significantly increases the average size of the synthesized particles. However, the investigation of the change in the dimensional characteristics of the produced clusters depending on the intensity of the buffer-gas flow faced serious difficulties. The obtained results differ significantly from the earlier experiments on the synthesis of the transition-metal oxides. In order to solve this contradiction, the computer simulation of the condensation of copper atoms from the gas phase with three different cooling rates and two final temperatures T = 373 K and T = 77 K has been performed. It has been discovered that the cooling rate of the gas mixture and the final temperature directly influence the quantity and size of the produced particles. Thus, at a tenfold lower cooling rate, the average number of particles increases 2.7 times at a final temperature of 77 K and by 3.1 times at T = 373 K.

  19. Visible and ultraviolet spectroscopy of gas phase rhodamine 575 cations.

    Science.gov (United States)

    Daly, Steven; Kulesza, Alexander; Knight, Geoffrey; MacAleese, Luke; Antoine, Rodolphe; Dugourd, Philippe

    2015-06-04

    The visible and ultraviolet spectroscopy of gas phase rhodamine 575 cations has been studied experimentally by action-spectroscopy in a modified linear ion trap between 220 and 590 nm and by time-dependent density functional theory (TDDFT) calculations. Three bands are observed that can be assigned to the electronic transitions S0 → S1, S0 → S3, and S0 → (S8,S9) according to the theoretical prediction. While the agreement between theory and experiment is excellent for the S3 and S8/S9 transitions, a large shift in the value of the calculated S1 transition energy is observed. A theoretical analysis of thermochromism, potential vibronic effects, and-qualitatively-electron correlation revealed it is mainly the latter that is responsible for the failure of TDDFT to accurately reproduce the S1 transition energy, and that a significant thermochromic shift is also present. Finally, we investigated the nature of the excited states by analyzing the excitations and discussed their different fragmentation behavior. We hypothesize that different contributions of local versus charge transfer excitations are responsible for 1-photon versus 2-photon fragmentation observed experimentally.

  20. Surface plasmon sensing of gas phase contaminants using optical fiber.

    Energy Technology Data Exchange (ETDEWEB)

    Thornberg, Steven Michael; White, Michael I.; Rumpf, Arthur Norman; Pfeifer, Kent Bryant

    2009-10-01

    Fiber-optic gas phase surface plasmon resonance (SPR) detection of several contaminant gases of interest to state-of-health monitoring in high-consequence sealed systems has been demonstrated. These contaminant gases include H{sub 2}, H{sub 2}S, and moisture using a single-ended optical fiber mode. Data demonstrate that results can be obtained and sensitivity is adequate in a dosimetric mode that allows periodic monitoring of system atmospheres. Modeling studies were performed to direct the design of the sensor probe for optimized dimensions and to allow simultaneous monitoring of several constituents with a single sensor fiber. Testing of the system demonstrates the ability to detect 70mTorr partial pressures of H{sub 2} using this technique and <280 {micro}Torr partial pressures of H{sub 2}S. In addition, a multiple sensor fiber has been demonstrated that allows a single fiber to measure H{sub 2}, H{sub 2}S, and H{sub 2}O without changing the fiber or the analytical system.

  1. The Influence of Mixing in High Temperature Gas Phase Reactions

    DEFF Research Database (Denmark)

    Østberg, Martin

    1996-01-01

    by injection of NH3 with carrier gas into the flue gas. NH3 can react with NO and form N2, but a competing reaction path is the oxidation of NH3 to NO.The SNR process is briefly described and it is shown by chemical kinetic modelling that OH radicals under the present conditions will initiate the reaction...... diffusion. The SNR process is simulated using the mixing model and an empirical kinetic model based on laboratory experiments.A bench scale reactor set-up has been built using a natural gas burner to provide the main reaction gas. The set-up has been used to perform an experimental investigation......The objective of this thesis is to describe the mixing in high temperature gas phase reactions.The Selective Non-Catalytic Reduction of NOx (referred as the SNR process) using NH3 as reductant was chosen as reaction system. This in-furnace denitrification process is made at around 1200 - 1300 K...

  2. Gas phase plasma impact on phenolic compounds in pomegranate juice.

    Science.gov (United States)

    Herceg, Zoran; Kovačević, Danijela Bursać; Kljusurić, Jasenka Gajdoš; Jambrak, Anet Režek; Zorić, Zoran; Dragović-Uzelac, Verica

    2016-01-01

    The aim of the study was to evaluate the effect of gas phase plasma on phenolic compounds in pomegranate juice. The potential of near infrared reflectance spectroscopy combined with partial least squares for monitoring the stability of phenolic compounds during plasma treatment was explored, too. Experiments are designed to investigate the effect of plasma operating conditions (treatment time 3, 5, 7 min; sample volume 3, 4, 5 cm(3); gas flow 0.75, 1, 1.25 dm(3) min(-1)) on phenolic compounds and compared to pasteurized and untreated pomegranate juice. Pasteurization and plasma treatment resulted in total phenolic content increasing by 29.55% and 33.03%, respectively. Principal component analysis and sensitivity analysis outputted the optimal treatment design with plasma that could match the pasteurized sample concerning the phenolic stability (5 min/4 cm(3)/0.75 dm(3) min(-1)). Obtained results demonstrate the potential of near infrared reflectance spectroscopy that can be successfully used to evaluate the quality of pomegranate juice upon plasma treatment considering the phenolic compounds.

  3. Atomic and molecular physics in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Toburen, L.H.

    1990-09-01

    The spatial and temporal distributions of energy deposition by high-linear-energy-transfer radiation play an important role in the subsequent chemical and biological processes leading to radiation damage. Because the spatial structures of energy deposition events are of the same dimensions as molecular structures in the mammalian cell, direct measurements of energy deposition distributions appropriate to radiation biology are infeasible. This has led to the development of models of energy transport based on a knowledge of atomic and molecular interactions process that enable one to simulate energy transfer on an atomic scale. Such models require a detailed understanding of the interactions of ions and electrons with biologically relevant material. During the past 20 years there has been a great deal of progress in our understanding of these interactions; much of it coming from studies in the gas phase. These studies provide information on the systematics of interaction cross sections leading to a knowledge of the regions of energy deposition where molecular and phase effects are important and that guide developments in appropriate theory. In this report studies of the doubly differential cross sections, crucial to the development of stochastic energy deposition calculations and track structure simulation, will be reviewed. Areas of understanding are discussed and directions for future work addressed. Particular attention is given to experimental and theoretical findings that have changed the traditional view of secondary electron production for charged particle interactions with atomic and molecular targets.

  4. Germanium-silicon alloy and core-shell nanocrystals by gas phase synthesis.

    Science.gov (United States)

    Mehringer, Christian; Kloner, Christian; Butz, Benjamin; Winter, Benjamin; Spiecker, Erdmann; Peukert, Wolfgang

    2015-03-12

    In this work we present a novel route to synthesize well defined germanium-silicon alloy (GexSi1-x) and core-shell nanocrystals (NCs) employing monosilane (SiH4) and monogermane (GeH4) as precursors in a continuously operated two-stage hot-wall aerosol reactor setup. The first hot-wall reactor stage (HWR I) is used to produce silicon (Si) seed particles from SiH4 pyrolysis in Argon (Ar). The resulting seeding aerosol is fed into the second reactor stage (HWR II) and a mixture of SiH4 and GeH4 is added. The ratio of the precursors in the feed, their partial pressures, the synthesis temperature in HWR II and the overall pressure are varied depending on the desired morphology and composition. Alloy particle production is achieved in the heterogeneous surface reaction regime, meaning that germanium (Ge) and Si are deposited on the seed surface simultaneously. The NCs can be synthesized with any desired composition, whilst maintaining a mean diameter around 30 nm with a geometric standard deviation (GSD) around 1.25. The absorption behavior and the related fundamental optical band gap energy in dependence on the alloy composition are exemplarily presented. They prove the possibility to tailor NC properties for electronical and opto-electronical applications. In the homogeneous gas phase reaction regime facetted Ge-Si core-shell structures are accessible. The Ge deposition on the seeds precedes the Si deposition due to different gas phase reaction kinetics of the precursors. The Si layer grows epitaxially on the Ge core and is around 5 nm thick.

  5. Development of Peptide Nanotube-Modified Biosensors for Gas-Phase Organophosphate Detection

    Science.gov (United States)

    2013-03-01

    Chemistry, vol. 78: 835-843, 2006. 23. Marrs, T. C., Organophosphate Poisoning , Pharmaceutical Therapy, vol. 58: 51- 66, 1993. 24. Mlsna, T. E...DEVELOPMENT OF PEPTIDE NANOTUBE-MODIFIED BIOSENSORS FOR GAS-PHASE ORGANOPHOSPHATE DETECTION...States. AFIT-ENV-13-M-35 DEVELOPMENT OF PEPTIDE NANOTUBE-MODIFIED BIOSENSORS FOR GAS-PHASE ORGANOPHOSPHATE DETECTION THESIS Presented

  6. A stable aminothioketyl radical in the gas phase.

    Science.gov (United States)

    Zimnicka, Magdalena; Gregersen, Joshua A; Tureček, František

    2011-07-06

    We report the first preparation of a stable aminothioketyl radical, CH(3)C(•)(SH)NHCH(3) (1), by fast electron transfer to protonated thioacetamide in the gas phase. The radical was characterized by neutralization-reionization mass spectrometry and ab initio calculations at high levels of theory. The unimolecular dissociations of 1 were elucidated with deuterium-labeled radicals CH(3)C(•)(SD)NHCH(3) (1a), CH(3)C(•)(SH)NDCH(3) (1b), CH(3)C(•)(SH)NHCD(3) (1c), and CD(3)C(•)(SH)NHCH(3) (1d). The main dissociations of 1 were a highly specific loss of the thiol H atom and a specific loss of the N-methyl group, which were competitive on the potential energy surface of the ground electronic state of the radical. RRKM calculations on the CCSD(T)/aug-cc-pVTZ potential energy surface indicated that the cleavage of the S-H bond in 1 dominated at low internal energies, E(int) < 232 kJ mol(-1). The cleavage of the N-CH(3) bond was calculated to prevail at higher internal energies. Loss of the thiol hydrogen atom can be further enhanced by dissociations originating from the B excited state of 1 when accessed by vertical electron transfer. Hydrogen atom addition to the thioamide sulfur atom is calculated to have an extremely low activation energy that may enable the thioamide group to function as a hydrogen atom trap in peptide radicals. The electronic properties and reactivity of the simple aminothioketyl radical reported here may be extrapolated and applied to elucidate the chemistry of thioxopeptide radicals and cation radicals of interest to protein structure studies.

  7. Histidine-containing radicals in the gas phase.

    Science.gov (United States)

    Turecek, Frantisek; Yao, Chunxiang; Fung, Y M Eva; Hayakawa, Shigeo; Hashimoto, Mami; Matsubara, Hiroshi

    2009-05-21

    Radicals containing the histidine residue have been generated in the gas phase by femtosecond electron transfer to protonated histidine-N-methylamide (1H+), Nalpha-acetylhistidine-N-methylamide (2H+), Nalpha-glycylhistidine (3H+), and Nalpha-histidylglycine (4H+). Radicals generated by collisional electron transfer from dimethyldisulfide to ions 1H+ and 2H+ at 7 keV collision energies were found to dissociate completely on the microsecond time scale, as probed by reionization to cations. The main dissociations produced fragments from the imidazole side chain and the cleavage of the C(alpha)CO bond, whereas products of NCalpha bond cleavage were not observed. Electron transfer from gaseous potassium atoms to ions 3H+ and 4H+ at 2.97 keV collision energies not only caused backbone NCalpha bond dissociations but also furnished fractions of stable radicals that were detected after conversion to anions. Ion structures, ion-electron recombination energies, radical structures, electron affinities, and dissociation and transition-state energies were obtained by combined density functional theory and Møller-Plesset perturbational calculations (B3-PMP2) and basis sets ranging from 6-311+G(2d,p) to aug-cc-pVTZ. The Rice-Ramsperger-Kassel-Marcus theory was used to calculate rate constants on the B3-PMP2 potential energy surfaces to aid interpretation of the mass spectrometric data. The stability of Nalpha-histidylglycine-derived radicals is attributed to an exothermic isomerization in the imidazole ring, which is internally catalyzed by reversible proton transfer from the carboxyl group. The isomerization depends on the steric accessibility of the histidine side chain and the carboxyl group and involves a novel cation radical-COO salt-bridge intermediate.

  8. CHAOS III: Gas-phase Abundances in NGC 5457

    Science.gov (United States)

    Croxall, Kevin V.; Pogge, Richard W.; Berg, Danielle A.; Skillman, Evan D.; Moustakas, John

    2016-10-01

    We present Large Binocular Telescope observations of 109 H ii regions in NGC 5457 (M101) obtained with the Multi-Object Double Spectrograph. We have robust measurements of one or more temperature-sensitive auroral emission lines for 74 H ii regions, permitting the measurement of “direct” gas-phase abundances. Comparing the temperatures derived from the different ionic species, we find: (1) strong correlations of T[N ii] with T[S iii] and T[O iii], consistent with little or no intrinsic scatter; (2) a correlation of T[S iii] with T[O iii], but with significant intrinsic dispersion; (3) overall agreement between T[N ii], T[S ii], and T[O ii], as expected, but with significant outliers; (4) the correlations of T[N ii] with T[S iii] and T[O iii] match the predictions of photoionization modeling while the correlation of T[S iii] with T[O iii] is offset from the prediction of photoionization modeling. Based on these observations, which include significantly more observations of lower excitation H ii regions, missing in many analyses, we inspect the commonly used ionization correction factors (ICFs) for unobserved ionic species and propose new empirical ICFs for S and Ar. We have discovered an unexpected population of H ii regions with a significant offset to low values in Ne/O, which defies explanation. We derive radial gradients in O/H and N/O which agree with previous studies. Our large observational database allows us to examine the dispersion in abundances, and we find intrinsic dispersions of 0.074 ± 0.009 in O/H and 0.095 ± 0.009 in N/O (at a given radius). We stress that this measurement of the intrinsic dispersion comes exclusively from direct abundance measurements of H ii regions in NGC 5457.

  9. Measurement of Gas-phase Acids in Diesel Exhaust

    Science.gov (United States)

    Wentzell, J. J.; Liggio, J.; Li, S.; Vlasenko, A. L.; Staebler, R. M.; Brook, J.; Lu, G.; Poitras, M.; Chan, T.

    2012-12-01

    Gas-phase acids were measured using chemical ionization mass spectrometry (CIMS) as part of the Diesel Engine Emission Research Experiment (DEERE). The CIMS technique, utilizing acetate ion (CH3COO-) as a reagent ion, proved to be a rapid (measurements on the order of seconds) and sensitive (several counts/pptv) method of quantifying the acid emissions. Diluted diesel exhaust measurements were made from a Constant Volume Sampling dilution tunnel using a light duty (1.9L turbocharged Volkswagen Jetta TDI) diesel engine equipped with an OEM diesel oxidation catalyst and exhaust gas recirculation, mounted on an engine dynamometer. Acids measured included isocyanic, nitrous, nitric, propionic and sum of lactic and oxalic, as well as other unidentified compounds. Complimentary measurements of CO, CO2, Total Hydrocarbon (THC), and NOx, were also performed. Several engine modes (different engine rpm and torque outputs) at steady state were examined to determine their effect on acid emissions. Emission rates with respect to NOx and fuel based emission factors were determined. Measurements of HONO fuel emission factors agree well with real-world measurements within a traffic tunnel.1 The first estimate of isocyanic acid emission factors from a diesel engine is reported, and suggests that the emission of this highly toxic compound in diesel exhaust should not be ignored. 1. Kurtenbach, R., Becker, K. H., Gomes, J. A. G., Kleffmann, J.,Lorzer, J. C., Spittler, M., Wiesen, P., Ackermann, R., Geyer, A.,and Platt, U.: Investigations of emissions and heterogeneous formation of HONO in a road traffic tunnel, Atmos. Environ., 35, 3385-3394, doi:10.1016/S1352-2310(01)00138-8, 2001.

  10. Gas-Phase Combustion Synthesis of Nonoxide Nanoparticles in Microgravity

    Science.gov (United States)

    Axelbaum, R. L.; Kumfer, B. M.; Sun, Z.; Chao, B. H.

    2001-01-01

    Gas-phase combustion synthesis is a promising process for creating nanoparticles for the growing nanostructure materials industry. The challenges that must be addressed are controlling particle size, preventing hard agglomerates, maintaining purity, and, if nonoxides are synthesized, protecting the particles from oxidation and/or hydrolysis during post-processing. Sodium-halide Flame Encapsulation (SFE) is a unique methodology for producing nonoxide nanoparticles that addresses these challenges. This flame synthesis process incorporates sodium and metal-halide chemistry, resulting in nanoparticles that are encapsulated in salt during the early stages of their growth in the flame. Salt encapsulation has been shown to allow control of particle size and morphology, while serving as an effective protective coating for preserving the purity of the core particles. Metals and compounds that have been produced using this technology include Al, W, Ti, TiB2, AlN, and composites of W-Ti and Al-AlN. Oxygen content in SFE synthesized nano- AlN has been measured by neutron activation analysis to be as low as 0.54wt.%, as compared to over 5wt.% for unprotected AlN of comparable size. The overall objective of this work is to study the SFE process and nano-encapsulation so that they can be used to produce novel and superior materials. SFE experiments in microgravity allow the study of flame and particle dynamics without the influence of buoyancy forces. Spherical sodium-halide flames are produced in microgravity by ejecting the halide from a spherical porous burner into a quiescent atmosphere of sodium vapor and argon. Experiments are performed in the 2.2 sec Drop Tower at the NASA-Glenn Research Center. Numerical models of the flame and particle dynamics were developed and are compared with the experimental results.

  11. Gas-Phase Combustion Synthesis of Aluminum Nitride Powder

    Science.gov (United States)

    Axelbaum, R. L.; Lottes, C. R.; Huertas, J. I.; Rosen, L. J.

    1996-01-01

    Due to its combined properties of high electrical resistivity and high thermal conductivity aluminum nitride (AlN) is a highly desirable material for electronics applications. Methods are being sought for synthesis of unagglomerated, nanometer-sized powders of this material, prepared in such a way that they can be consolidated into solid compacts having minimal oxygen content. A procedure for synthesizing these powders through gas-phase combustion is described. This novel approach involves reacting AlCl3, NH3, and Na vapors. Equilibrium thermodynamic calculations show that 100% yields can be obtained for these reactants with the products being AlN, NaCl, and H2. The NaCl by-product is used to coat the AlN particles in situ. The coating allows for control of AlN agglomeration and protects the powders from hydrolysis during post-flame handling. On the basis of thermodynamic and kinetic considerations, two different approaches were employed to produce the powder, in co-flow diffusion flame configurations. In the first approach, the three reactants were supplied in separate streams. In the second, the AlCl3 and NH3 were premixed with HCl and then reacted with Na vapor. X-ray diffraction (XRD) spectra of as-produced powders show only NaCl for the first case and NaCl and AlN for the second. After annealing at 775 C tinder dynamic vacuum, the salt was removed and XRD spectra of powders from both approaches show only AlN. Aluminum metal was also produced in the co-flow flame by reacting AlCl3 with Na. XRD spectra of as-produced powders show the products to be only NaCl and elemental aluminum.

  12. Uridine Nucleoside Thiation: Gas-Phase Structures and Energetics

    Science.gov (United States)

    Hamlow, Lucas; Lee, Justin; Rodgers, M. T.; Berden, Giel; Oomens, Jos

    2016-06-01

    The naturally occurring thiated uridine nucleosides, 4-thiouridine (s4Urd) and 2-thiouridine (s2Urd), play important roles in the function and analysis of a variety of RNAs. 2-Thiouridine and its C5 modified analogues are commonly found in tRNAs and are believed to play an important role in codon recognition possibly due to their different structure, which has been shown by NMR to be predominantly C3'-endo. 2-Thiouridine may also play an important role in facilitating nonenzymatic RNA replication and transcription. 4-Thiouridine is a commonly used photoactivatable crosslinker that is often used to study RNA-RNA and RNA-protein cross-linking behavior. Differences in the base pairing between uracil and 4-thiouracil with adenine and guanine are an important factor in their role as a cross linker. The photoactivity of s4Urd may also aid in preventing near-UV lethality in cells. An understanding of their intrinsic structure in the gas-phase may help further elucidate the roles these modified nucleosides play in the regulation of RNAs. In this work, infrared multiple photon dissociation (IRMPD) action spectra of the protonated forms of s2Urd and s4Urd were collected in the IR fingerprint region. Structural information is determined by comparison with theoretical linear IR spectra generated from density functional theory calculations using molecular modeling to generate low-energy candidate structures. Present results are compared with analogous results for the protonated forms of uridine and 2'-deoxyuridine as well as solution phase NMR data and crystal structures.

  13. Gas phase depletion and flow dynamics in horizontal MOCVD reactors

    Science.gov (United States)

    Van de Ven, J.; Rutten, G. M. J.; Raaijmakers, M. J.; Giling, L. J.

    1986-08-01

    Growth rates of GaAs in the MOCVD process have been studied as a function of both lateral and axial position in horizontal reactor cells with rectangular cross-sections. A model to describe growth rates in laminar flow systems on the basis of concentration profiles under diffusion controlled conditions has been developed. The derivation of the growth rate equations includes the definition of an entrance length for the concentration profile to developed. In this region, growth rates appear to decrease with the 1/3 power of the axial position. Beyond this region, an exponential decrease is found. For low Rayleigh number conditions, the present experimental results show a very satisfactory agreement with the model without parameter fitting for both rectangular and tapered cells, and with both H 2 and N 2 as carrier gases. Theory also predicts that uniform deposition can be obtained over large areas in the flow direction for tapered cells, which has indeed been achieved experimentally. The influence of top-cooling in the present MOCVD system has been considered in more detail. From the experimental results, conclusions could be drawn concerning the flow characteristics. For low Rayleigh numbers (present study ≲ 700) it follows that growth rate distributions correspond with forced laminar flow characteristics. For relatively high Rayleigh numbers (present work 1700-2800), free convective effects with vortex formation are important. These conclusions are not specific for the present system, but apply to horizontal cold-wall reactors in general. On the basis of the present observations, recommendations for a cell design to obtain large area homogeneous deposition have been formulated. In addition, this work supports the conclusion that the final decomposition of trimethylgallium in the MOCVD process mainly takes place at the hot substrate and susceptor and not in the gas phase.

  14. Chemical models of interstellar gas-grain processes. II - The effect of grain-catalysed methane on gas phase evolution

    Science.gov (United States)

    Brown, Paul D.; Charnley, S. B.

    1991-01-01

    The effects on gas phase chemistry which result from the continuous desorption of methane molecules from grain surfaces are studied. Significant and sustained enhancements in the abundances of several complex hydrocarbon molecules are found, in good agreement with their observed values in TMC-1. The overall agreement is, however, just as good for the case of zero CH4 desorption efficiency. It is thus impossible to determine from the models whether or not the grain-surface production of methane is responsible for the observed abundances of some hydrocarbon molecules.

  15. Importance of the gas phase role to the prediction of energetic material behavior: An experimental study

    Science.gov (United States)

    Ali, A. N.; Son, S. F.; Asay, B. W.; Sander, R. K.

    2005-03-01

    Various thermal (radiative, conductive, and convective) initiation experiments are performed to demonstrate the importance of the gas phase role in combustion modeling of energetic materials (EM). A previously published condensed phase model that includes a predicted critical irradiance above which ignition is not possible is compared to experimental laser ignition results for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6-trinitrotoluene (TNT). Experimental results conflict with the predicted critical irradiance concept. The failure of the model is believed to result from a misconception about the role of the gas phase in the ignition process of energetic materials. The model assumes that ignition occurs at the surface and that evolution of gases inhibits ignition. High speed video of laser ignition, oven cook-off and hot wire ignition experiments captures the ignition of HMX and TNT in the gas phase. A laser ignition gap test is performed to further evaluate the effect of gas phase laser absorption and gas phase disruption on the ignition process. Results indicate that gas phase absorption of the laser energy is probably not the primary factor governing the gas phase ignition observations. It is discovered that a critical gap between an HMX pellet and a salt window of 6mm±0.4mm exists below which ignition by CO2 laser is not possible at the tested irradiances of 29W /cm2 and 38W/cm2 for HMX ignition. These observations demonstrate that a significant disruption of the gas phase, in certain scenarios, will inhibit ignition, independent of any condensed phase processes. These results underscore the importance of gas phase processes and illustrate that conditions can exist where simple condensed phase models are inadequate to accurately predict the behavior of energetic materials.

  16. Mm/submm Study of Gas-Phase Photoproducts from Methanol Interstellar Ice Analogues

    Science.gov (United States)

    Mesko, AJ; Smith, Houston Hartwell; Milam, Stefanie N.; Widicus Weaver, Susanna L.

    2016-06-01

    Icy grain reactions have gained quite the popularity in the astrochemistry community to explain the formation of complex organic molecules. Through temperature programmed desorption and photolysis experiments we use rotational spectroscopy to measure the gas-phase products of icy grain reactions. Previous results include testing detection limits of the system by temperature programmed desorption of methanol and water ices, photochemistry of gas-phase methanol, and detection of photodesorbed water from a pure water ice surface. Current work that will be discussed focuses on the detection of gas-phase CO and other photoproducts from an ice surface.

  17. The gas-phase thermal chemistry of tetralin and related model systems

    Energy Technology Data Exchange (ETDEWEB)

    Malandra, J.

    1993-05-01

    The thesis is divided into 5 papers: gas-phase thermal decomposition of tetralin; flash vacuum pyrolysis of 3-benzocycloheptenone and 1,3, 4,5-tetrahydro-2-benzothiepin-2,2-dioxide (model systems for gas-phase pyrolysis of tetralin); high-temperature gas-phase reactions of o-allylbenzyl radicals generated by flash vacuum pyrolysis of is(o-allylbenzyl) oxalate; flash vacuum pyrolysis of 1,4-diphenylbutane; and flash vacuum pyrolysis of o-allyltoluene, o-(3-butenyl)toluene and o-(pentenyl)toluene were also used.

  18. [N,N-Bis(diphenyl-phosphino)isopropyl-amine]dibromidonickel(II).

    Science.gov (United States)

    Hapke, Marko; Wöhl, Anina; Peitz, Stephan; Müller, Bernd H; Spannenberg, Anke; Rosenthal, Uwe

    2009-02-06

    The title compound, [NiBr(2)(C(27)H(27)NP(2))], was synthesized by the reaction of NiBr(2)(dme) (dme is 1,2-dimethoxy-ethane) with N,N-bis-(diphenyl-phosphino)isopropyl-amine in methanol/tetra-hydro-furan. The nickel(II) center is coordinated by two P atoms of the chelating PNP ligand, Ph(2)PN(iPr)PPh(2), and two bromide ions in a distorted square-planar geometry.

  19. Theoretical Study on Gas—phase Pyrolytic Reactions of N—Ethyl,Isopropyl and N—t—Butyl Substituted 2—Aminopyrazine

    Institute of Scientific and Technical Information of China (English)

    洪三国; 陈丽萍

    2003-01-01

    Density functional theory(DFT)and ab initio methods were used to study gas-phase pyrolytic reaction mechanisms of N-ethyl,N-isopropyl and N-t-butyl substituted 2-aminopyrazine at B3LYP/6-31G* and MP2/6-31G*,respectively,Single-point energies of all optimized molecular geometries were calculated at B3LYP/6-311 G(2d,p)level.Results show that the pyrolytic reactions which were caused by the migration of atom H(17) via a six-member ring transiton state.The activation energies which were verified by vibrational analysis and correlated with zero-point energies along the reaction channel atB3LYP/6-3110 G(2d,p)level were 252.02kJ·mol-1(N-ethyl substituted),235.92kJ·mol-1(N-isopropyl substituted)and 234.27kJ·mol-1(N-t-butyl substituted),respectively.The results were in good agreement with available experimental data.

  20. Fluorescence resonance energy transfer of gas-phase ions under ultra high vacuum and ambient conditions.

    Science.gov (United States)

    Frankevich, Vladimir; Chagovets, Vitaliy; Widjaja, Fanny; Barylyuk, Konstantin; Yang, Zhiyi; Zenobi, Renato

    2014-05-21

    We report evidence for fluorescence resonance energy transfer (FRET) of gas-phase ions under ultra high vacuum conditions (10(-9) mbar) inside a mass spectrometer as well as under ambient conditions inside an electrospray plume. Two different FRET pairs based on carboxyrhodamine 6G (donor) and ATTO590 or Bodipy TR (acceptor) dyes were examined and their gas-phase optical properties were studied. Our measurements indicate a different behavior for the two FRET pairs, which can be attributed to their different conformations in the gas phase. Upon desolvation via electrospray ionization, one of the FRET pairs undergoes a conformational change that leads to disappearance of FRET. This study shows the promise of FRET to obtain a direct correlation between solution and gas-phase structures.

  1. Recent Results on Fast Flow Gas-Phase Partial Oxidation of Lower Alkanes

    Institute of Scientific and Technical Information of China (English)

    Vladimir S. Arutyunov

    2004-01-01

    Recent experimental results and kinetic modeling of fast flow gas-phase oxidation of methane and other lower alkanes to methanol and other oxygenates are discussed, alongside with prospects and possible areas for applications of the processes.

  2. Gas phase ion chemistry of coumarins: ab initio calculations used to ...

    African Journals Online (AJOL)

    Gas phase ion chemistry of coumarins: ab initio calculations used to justify ... and quadrupole mass spectrometer (qMS) coupled to a gas chromatograph is ... Ab Initio calculations, Electron ionization, Positive chemical ionization, Negative ...

  3. Ultrafast electronic relaxation of excited state vitamin B{sub 12} in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Shafizadeh, Niloufar [Laboratoire de Photophysique Moleculaire, U.P.R. 3361 CNRS Bat 210, Universite de Paris-Sud, 91405 Orsay, Cedex (France)], E-mail: Niloufar.Shafizadeh@u-psud.fr; Poisson, Lionel; Soep, Benoit [Laboratoire Francis Perrin, CEA/DSM/DRECAM/SPAM - CNRS URA 2453, CEA Saclay, 91191 Gif-sur-Yvette Cedex (France)

    2008-06-23

    The time evolution of electronically excited vitamin B{sub 12} (cyanocobalamin) has been observed for the first time in the gas phase. It reveals an ultrafast decay to a state corresponding to metal excitation. This decay is interpreted as resulting from a ring to metal electron transfer. This opens the observation of the excited state of other complex biomimetic systems in the gas phase, the key to the characterisation of their complex evolution through excited electronic states.

  4. Ultrafast electronic relaxation of excited state vitamin B 12 in the gas phase

    Science.gov (United States)

    Shafizadeh, Niloufar; Poisson, Lionel; Soep, Benoıˆt

    2008-06-01

    The time evolution of electronically excited vitamin B 12 (cyanocobalamin) has been observed for the first time in the gas phase. It reveals an ultrafast decay to a state corresponding to metal excitation. This decay is interpreted as resulting from a ring to metal electron transfer. This opens the observation of the excited state of other complex biomimetic systems in the gas phase, the key to the characterisation of their complex evolution through excited electronic states.

  5. Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth Reactions

    Science.gov (United States)

    2013-09-19

    DOI: 10.1021/ct1000268. 26. A. J. Midey, T. M. Miller, A. A. Viggiano, N. C. Bera, S. Maeda, and K. Morokuma, Chemistry of VX Surrogates and Ion...THEORETICAL STUDIES OF GAS PHASE ELEMENTARY AND CARBON NANOSTRUCTURE GROWTH REACTIONS KEIJI MOROKUMA EMORY UNIVERSITY 09/19/2013 Final Report...Z39.18 30-09-2013 Final Performance Report 1 July 2010 - 30 June 2013 Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth

  6. Gas Phase Polymerization of Ethylene with Supported Titanium-Nickel Catalysts

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A new ditransition-metal catalyst system TiCl4-NiCl2/MgCl2-SiO2/AlR3 was prepared.Gas phase polymerization of ethylene with the catalysts has been studied.The kinetic curves of gas phase polymerization showed a decline.The catalystic efficiency and polymerization reaction rates have a optimum value when Ni content of the catalysts was 12.5%(mol).The products obtained are branched polyethylene.

  7. An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

    Science.gov (United States)

    Koontz, Steven L.; Davis, Dennis D.; Hansen, Merrill

    1988-01-01

    A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

  8. Gas-Phase Molecular Dynamics: High Resolution Spectroscopy and Collision Dynamics of Transient Species

    Energy Technology Data Exchange (ETDEWEB)

    Hall,G.E.; Sears, T.J.

    2009-04-03

    This research is carried out as part of the Gas-Phase Molecular Dynamics program in the Chemistry Department at Brookhaven National Laboratory. High-resolution spectroscopy, augmented by theoretical and computational methods, is used to investigate the structure and collision dynamics of chemical intermediates in the elementary gas-phase reactions involved in combustion chemistry. Applications and methods development are equally important experimental components of this work.

  9. Gas-Phase Molecular Dynamics: High Resolution Spectroscopy and Collision Dynamics of Transient Species

    Energy Technology Data Exchange (ETDEWEB)

    Hall, G.E.

    2011-05-31

    This research is carried out as part of the Gas-Phase Molecular Dynamics program in the Chemistry Department at Brookhaven National Laboratory. Chemical intermediates in the elementary gas-phase reactions involved in combustion chemistry are investigated by high resolution spectroscopic tools. Production, reaction, and energy transfer processes are investigated by transient, double resonance, polarization and saturation spectroscopies, with an emphasis on technique development and connection with theory, as well as specific molecular properties.

  10. Moisture effects on greenhouse gases generation in nitrifying gas-phase compost biofilters.

    Science.gov (United States)

    Maia, Guilherme D N; Day, George B; Gates, Richard S; Taraba, Joseph L; Coyne, Mark S

    2012-06-01

    Gas-phase compost biofilters are extensively used in concentrated animal feeding operations to remove odors and, in some cases, ammonia from air sources. The expected biochemical pathway for these predominantly aerobic systems is nitrification. However, non-uniform media with low oxygen levels can shift biofilter microbial pathways to denitrification, a source of greenhouse gases. Several factors contribute to the formation of anoxic/anaerobic zones: media aging, media and particle structure, air velocity distribution, compaction, biofilm thickness, and moisture content (MC) distribution. The present work studies the effects of media moisture conditions on ammonia (NH(3)) removal and greenhouse gas generation (nitrous oxide, N(2)O and methane, CH(4)) for gas-phase compost biofilters subject to a 100-day controlled drying process. Continuous recordings were made for the three gases and water vapor (2.21-h sampling cycle, each cycle consisted of three gas species, and water vapor, for a total of 10,050 data points). Media moisture conditions were classified into three corresponding media drying rate (DR) stages: Constant DR (wetter media), falling DR, and stable-dry system. The first-half of the constant DR period (0-750 h; MC=65-52%, w.b.) facilitated high NH(3) removal rates, but higher N(2)O generation and no CH(4) generation. At the drier stages of the constant DR (750-950 h; MC=52-48%, w.b.) NH(3) removal remained high but N(2)O net generation decreased to near zero. In the falling DR stage (1200-1480 h; MC=44-13%) N(2)O generation decreased, CH(4) increased, and NH(3) was no longer removed. No ammonia removal or greenhouse gas generation was observed in the stable-dry system (1500-2500 h; MC=13%). These results indicate that media should remain toward the drier region of the constant DR (in close proximity to the falling DR stage; MC=50%, approx.), to maintain high levels of NH(3) removal, reduced levels of N(2)O generation, and nullify levels of CH(4

  11. Formation of Secondary Particulate Matter by Reactions of Gas Phase Hexanal with Sulfate Aerosol Particles

    Science.gov (United States)

    Zhang, J.

    2003-12-01

    The formation of secondary particulate matter from the atmospheric oxidation of organic compounds can significantly contribute to the particulate burden, but the formation of organic secondary particulate matter is poorly understood. One way of producing organic secondary particulate matter is the oxidation of hydrocarbons with seven or more carbon atoms to get products with low vapor pressure. However, several recent reports suggest that relatively low molecular weight carbonyls can enter the particle phase by undergoing heterogeneous reactions. This may be a very important mechanism for the formation of organic secondary particulate matter. Atmospheric aldehydes are important carbonyls in the gas phase, which form via the oxidation of hydrocarbons emitted from anthropogenic and biogenic sources. In this poster, we report the results on particle growth by the heterogeneous reactions of hexanal. A 5 L Continuous Stirred Tank Reactor (CSTR) is set up to conduct the reactions in the presence of seed aerosol particles of deliquesced ammonia bisulfate. Hexanal is added into CSTR by syringe pump, meanwhile the concentrations of hexanal are monitored with High Pressure Liquid Chromatograph (HPLC 1050). A differential Mobility Analyzer (TSI 3071) set to an appropriate voltage is employed to obtain monodisperse aerosols, and another DMA associated with a Condensation Nuclear Counter (TSI 7610) is used to measure the secondary particle size distribution by the reaction in CSTR. This permits the sensitive determination of particle growth due to the heterogeneous reaction, very little growth occurs when hexanal added alone. Results for the simultaneous addition of hexanal and alcohols will also be presented.

  12. Gas phase microreaction: nanomaterials synthesis via plasma exposure of liquid droplets

    Science.gov (United States)

    Maguire, Paul; Mahony, Charles; Kelsey, Colin; Hamilton, Neil; Askari, Sadegh; Macias-Montero, Manuel; Diver, Declan; Mariotti, Davide

    2015-09-01

    Plasma-liquid interactions are complex but offer considerable scope for use in nanomaterials synthesis. The introduction of individual picolitre micro-droplets into a steady-state low temperature plasma at atmospheric pressure, offers opportunities for enhanced scope and control of plasma-liquid chemistry and material properties. The gas-phase micro-reactor is similar in concept to liquid bubble microfluidics currently under intense research but with enhanced opportunities for scale-up. For nanomaterials and quantum dot synthesis, the addition of a liquid phase within the plasma expands considerably the scope for core-shell and alloy formation. The synthesis and encapsulation within a liquid droplet allows continuous delivery of nanoparticles to remote sites for plasma medicine, device fabrication or surface coating. We have synthesized Au nanoparticles in flight using AuHCl4 droplets with plasma flight times <0.1 ms. Also, Ag nanoparticles have been synthesized downstream via the delivery of plasma exposed water droplets onto AgNO3 laden substrates. Funding from EPSRC acknowledged (Grants EP/K006088/1 and EP/K006142/1).

  13. Metal-Organic Frameworks for Sensing Applications in the Gas Phase

    Directory of Open Access Journals (Sweden)

    Sabine Achmann

    2009-03-01

    Full Text Available Several metal-organic framework (MOF materials were under investigated to test their applicability as sensor materials for impedimetric gas sensors. The materials were tested in a temperature range of 120 °C - 240 °C with varying concentrations of O2, CO2, C3H8, NO, H2, ethanol and methanol in the gas atmosphere and under different test gas humidity conditions. Different sensor configurations were studied in a frequency range of 1 Hz -1 MHz and time-continuous measurements were performed at 1 Hz. The materials did not show any impedance response to O2, CO2, C3H8, NO, or H2 in the gas atmospheres, although for some materials a significant impedance decrease was induced by a change of the ethanol or methanol concentration in the gas phase. Moreover, pronounced promising and reversible changes in the electric properties of a special MOF material were monitored under varying humidity, with a linear response curve at 120 °C. Further investigations were carried out with differently doped MOF materials of this class, to evaluate the influence of special dopants on the sensor effect.

  14. Gas-phase CO2 subtraction for improved measurements of the organic aerosol mass concentration and oxidation degree by an aerosol mass spectrometer.

    Science.gov (United States)

    Collier, S; Zhang, Q

    2013-12-17

    The Aerodyne aerosol mass spectrometer (AMS) has been widely used for real-time characterization of the size-resolved chemical composition of sub-micrometer aerosol particles. The first step in AMS sampling is the pre-concentration of aerosols while stripping away the gas-phase components, which contributes to the high sensitivity of this instrument. The strength of the instrument lies in particle phase measurement; however, ion signals generated from gas-phase species can influence the interpretation of the particle-phase chemistry data. Here, we present methods for subtracting the varying contributions of gas-phase carbon dioxide (CO2) in the AMS spectra of aerosol particles, which is critical for determining the mass concentration and oxygen-to-carbon (O/C) ratio of organic aerosol. This report gives details on the gaseous CO2 subtraction analysis performed on a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) data set acquired from sampling of fresh and diluted vehicle emissions. Three different methods were used: (1) collocated continuous gas-phase CO2 measurement coupled with periodic filter tests consisting of sampling the same particle-free air by the AMS and the CO2 analyzer, (2) positive matrix factorization (PMF) analysis to separate the gas- and particle-phase signals of CO2(+) at m/z 44, and (3) use of the particle time-of-flight (PTOF) size-resolved chemical information for separation of gas- and particle-phase signals at m/z 44. Our results indicate that these three different approaches yield internally consistent values for the gas/particle apportionment of m/z 44, but methods 2 and 3 require certain conditions to be met to yield reliable results. The methods presented are applicable to any situation where gas-phase components may influence the PM signal of interest.

  15. Aerotaxy - A Gas-Phase Nanowire Growth Technique

    OpenAIRE

    Heurlin, Magnus

    2014-01-01

    In this thesis an efficient nanowire fabrication technique, called Aerotaxy, is investigated. Traditional nanowire fabrication techniques include the use of a substrate as a point of nanowire nucleation which limits the amount of nanowires that can be produced per unit time. In contrary, Aerotaxy offers a continuous growth process, in the gasphase, which could substantially increase the rate at which nanowires are fabricated and thus lower their fabrication cost. Investig...

  16. Formation of complex organic molecules in cold objects: the role of gas-phase reactions

    Science.gov (United States)

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-04-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

  17. Deposition of thin insulation layers from the gas phase

    Science.gov (United States)

    Behn, R.; Hagedorn, H.; Kammermaier, J.; Kobale, M.; Packonik, H.; Ristow, D.; Seebacher, G.

    1981-01-01

    The continuous deposition of thin organic dielectric films on metallized carrier foils by glow discharge in monomeric gases is described. Depending on the applied monomers, the films had a dissipation factor of .001 to .003 (1 kHz), a relative permittivity of 2.3 to 2.5 and a resistivity of about 10 to the 17th power omega cm. Additionally, they proved to have a high mechanical homogeneity. Self-healing rolled capacitors with a very high capacitance per volume and of consistently high quality were fabricated from the metallized carrier foils covered with the dielectric film.

  18. Influence of gas phase equilibria on the chemical vapor deposition of graphene.

    Science.gov (United States)

    Lewis, Amanda M; Derby, Brian; Kinloch, Ian A

    2013-04-23

    We have investigated the influence of gas phase chemistry on the chemical vapor deposition of graphene in a hot wall reactor. A new extended parameter space for graphene growth was defined through literature review and experimentation at low pressures (≥0.001 mbar). The deposited films were characterized by scanning electron microscopy, Raman spectroscopy, and dark field optical microscopy, with the latter showing promise as a rapid and nondestructive characterization technique for graphene films. The equilibrium gas compositions have been calculated across this parameter space. Correlations between the graphene films grown and prevalent species in the equilibrium gas phase revealed that deposition conditions associated with a high acetylene equilibrium concentration lead to good quality graphene deposition, and conditions that stabilize large hydrocarbon molecules in the gas phase result in films with multiple defects. The transition between lobed and hexagonal graphene islands was found to be linked to the concentration of the monatomic hydrogen radical, with low concentrations associated with hexagonal islands.

  19. Radical Reactions in the Gas Phase: Recent Development and Application in Biomolecules

    Directory of Open Access Journals (Sweden)

    Yang Gao

    2014-01-01

    Full Text Available This review summarizes recent literature describing the use of gas phase radical reactions for structural characterization of complex biomolecules other than peptides. Specifically, chemical derivatization, in-source chemical reaction, and gas phase ion/ion reactions have been demonstrated as effective ways to generate radical precursor ions that yield structural informative fragments complementary to those from conventional collision-induced dissociation (CID. Radical driven dissociation has been applied to a variety of biomolecules including peptides, nucleic acids, carbohydrates, and phospholipids. The majority of the molecules discussed in this review see limited fragmentation from conventional CID, and the gas phase radical reactions open up completely new dissociation channels for these molecules and therefore yield high fidelity confirmation of the structures of the target molecules. Due to the extensively studied peptide fragmentation, this review focuses only on nonpeptide biomolecules such as nucleic acids, carbohydrates, and phospholipids.

  20. Photoresponse of the protonated Schiff-base retinal chromophore in the gas phase

    DEFF Research Database (Denmark)

    Toker, Jonathan; Rahbek, Dennis Bo; Kiefer, H V

    2013-01-01

    The fragmentation, initiated by photoexcitation as well as collisionally-induced excitation, of several retinal chromophores was studied in the gas phase. The chromophore in the protonated Schiff-base form (RPSB), essential for mammalian vision, shows a remarkably selective photoresponse. The sel......The fragmentation, initiated by photoexcitation as well as collisionally-induced excitation, of several retinal chromophores was studied in the gas phase. The chromophore in the protonated Schiff-base form (RPSB), essential for mammalian vision, shows a remarkably selective photoresponse...... modifications of the chromophore. We propose that isomerizations play an important role in the photoresponse of gas-phase retinal chromophores and guide internal conversion through conical intersections. The role of protein interactions is then to control the specificity of the photoisomerization in the primary...

  1. Gamma-ray spectra of hexane in gas phase and liquid phase

    CERN Document Server

    Ma, Xiaoguang

    2012-01-01

    Theoretical gamma-ray spectra of molecule hexane have been calculated and compared with the experimental results in both gas (Surko et al, 1997) and liquid (Kerr et al, 1965) phases. The present study reveals that in gas phase not all valence electrons of hexane exhibit the same probability to annihilate a positron. Only the positrophilic electrons in the valence space dominate the gamma-ray spectra, which are in good agreement with the gas phase measurement. When hexane is confined in liquid phase, however, the intermolecular interactions ultimately eliminate the free molecular orientation and selectivity for the positrophilic electrons in the gas phase. As a result, the gamma-ray spectra of hexane become an averaged contribution from all valence electrons, which is again in agreement with liquid phase measurement. The roles of the positrophilic electrons in annihilation process for gas and liquid phases of hexane have been recognized for the first time in the present study.

  2. Oxidation of formic acid on the Pt(111) surface in the gas phase.

    Science.gov (United States)

    Gao, Wang; Keith, John A; Anton, Josef; Jacob, Timo

    2010-09-28

    Formic acid (HCOOH) oxidation on Pt(111) under gas-phase conditions is a benchmark heterogeneous catalysis reaction used to probe electro-catalytic HCOOH conversion in fuel cells, itself an important reaction in energy conversion. We used density functional theory (DFT) calculations to elucidate the fundamental oxidation mechanisms of HCOOH in the gas phase, determining the relative strengths of chemical interactions between HCOOH oxidation intermediates and the Pt(111) surface. We focused on investigating how water and adsorption coverage affects reaction intermediate structures and transition states. Our results show that adsorbed HCOO is a reactive intermediate in gas phase, and co-adsorbed water plays a key role in HCOOH oxidation influencing the structure of reaction intermediates and reaction barriers on Pt(111). The simulations show the preferred catalytic pathway is qualitatively dependent on surface coverage. These results provide a conceptual basis to better interpret its complicated experimental reaction kinetics.

  3. Dynamic Study of Polymer Particle Growth in Gas Phase Polymerization of Butadiene

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    An experimental apparatus composed of microscope, video camera. image-processing, and mini reactor which can be used for real-time measurement of the growth of polymer particle in gas phase polymerization was built up to carry out dynamic study of gas phase polymerization of butadiene by heterogeneous catalyst based on neodymium(Nd). The studies of the shape duplication of polymer particles and catalyst particles and the growth rate of polymer particle were made. Results show that the apparatus and procedure designed can be well utilized to make dynamic observation and data collection of the growth of polymer particle in gas phase polymerization. A phenomenon of shape duplication of polymer particles and catalyst particles was observed by the real-time measurement. The result also concludes that the activity of individual catalyst particle is different, and the effect of reaction pressure on the growth of polymer particle is significant.

  4. OMVPE growth and gas-phase reactions of AlGaN for UV emitters

    Energy Technology Data Exchange (ETDEWEB)

    Han, J.; Figiel, J.J.; Crawford, M.H.; Banas, M.A.; Bartram, M.E.; Biefeld, R.M. [Sandia National Labs., Albuquerque, NM (United States); Song, Y.K.; Nurmikko, A.V. [Brown Univ., Providence, RI (United States). Div. of Engineering

    1998-06-01

    Gas-phase parasitic reactions among TMG, TMA, and NH3, are investigated by monitoring of the growth rate/incorporation efficiency of GaN and AlN using an in-situ optical reflectometer. It is suggested that gas phase adduct (TMA: NH{sub 3}) reactions not only reduce the incorporation efficiency of TMA but also affect the incorporation behavior of TMGa. The observed phenomena can be explained by either a synergistic gas-phase scavenging effect or a surface site-blocking effect. Relatively low reactor pressures (30--50 Torr) are employed to grow an AlGaN/GaN QW p-n diode structure. The UV emission at 354 nm (FWHM {approximately} 6 nm) represents the first report of LED operation from an indium-free GaN QW diode.

  5. Do all the protic ionic liquids exist as molecular aggregates in the gas phase?

    Science.gov (United States)

    Zhu, Xiao; Wang, Yong; Li, Haoran

    2011-10-21

    According to an EI-MS study of 1,1,3,3-tetramethylguanidium-based protic ionic liquids (PILs), it has been concluded that not all PILs exist as molecular aggregates in the gas phase. The detection of both ions of m/z 115.0 and m/z 116.0 for the 1,1,3,3-tetramethylguanidinium trifluoromethylsulfonate (TMGS) protic ionic liquid indicates that both the molecular and ionic aggregates co-exist in the gas phase, which is to say that the TMGS may also evaporate via the ionic aggregates just like aprotic ionic liquids. Furthermore, investigation on triethylamine-based and 1-methylimidazole-based PILs confirmed that the gas phase structure of PILs depends on both the acidity and basicity of the corresponding acid and base.

  6. Device for two-dimensional gas-phase separation and characterization of ion mixtures

    Science.gov (United States)

    Tang, Keqi; Shvartsburg, Alexandre A.; Smith, Richard D.

    2006-12-12

    The present invention relates to a device for separation and characterization of gas-phase ions. The device incorporates an ion source, a field asymmetric waveform ion mobility spectrometry (FAIMS) analyzer, an ion mobility spectrometry (IMS) drift tube, and an ion detector. In one aspect of the invention, FAIMS operating voltages are electrically floated on top of the IMS drift voltage. In the other aspect, the FAIMS/IMS interface is implemented employing an electrodynamic ion funnel, including in particular an hourglass ion funnel. The present invention improves the efficiency (peak capacity) and sensitivity of gas-phase separations; the online FAIMS/IMS coupling creates a fundamentally novel two-dimensional gas-phase separation technology with high peak capacity, specificity, and exceptional throughput.

  7. Comparing gas-phase and grain-catalyzed H2 formation

    CERN Document Server

    Glover, S C O

    2003-01-01

    Because H2 formation on dust grain surfaces completely dominates gas-phase H2 formation in local molecular clouds, it is often assumed that gas-phase formation is never important. In fact, it is the dominant mechanism in a number of cases. In this paper, I briefly summarize the chemistry of gas-phase H2 formation, and show that it dominates for dust-to-gas ratios less than a critical value D_cr. I also show that D_cr is simple to calculate for any given astrophysical situation, and illustrate this with a number of examples, ranging from H2 formation in warm atomic gas in the Milky Way to the formation of protogalaxies at high redshift.

  8. Experimental study of Gas Phase Formation and Evolution in Low fO2 Planetary Basalts.

    Science.gov (United States)

    Rutherford, M. J.; Wetzel, D. T.; Saal, A. E.; Hauri, E. H.

    2012-12-01

    as 2CO = C +CO2 formed the graphite. Several series of experiments on chips of low fO2 glass created at high pressure quantify S, Cl and F partitioning into the H2O-CO gas phase with decompression steps from 200 to 40 MPa. A gas formed with the first pressure drop, indicating melt supersaturation with CO and/or CH4; H2O and lesser amounts of S, Cl and F partitioned into the initial gas, and continued to do so with additional drops in pressure. The ubiquitous Fe-metal seen in lunar picritic glasses may form by graphite oxidation, but also may form by breakdown of Fe(CO)5 as the melt continues to saturate during ascent. [1] A. E. Saal et al.(2008) Nature 454, 192-195. [2] E. H. Hauri et al (2011) Science 333, 213 -215. [3] Wetzel, D., Rutherford, M.J. Jacobsen S.D., Hauri, E.H., and Saal, A.E., (submitted); Nature Geoscience Aug. 1, 2012. [4] Zhang, C. and Duan, Z. (2009) GCA, 73, 2089-2102.

  9. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Hongying; Huang, Guangming, E-mail: gmhuang@ustc.edu.cn

    2015-03-31

    Graphical abstract: Direct and humidity independent mass spectrometry analysis of gas phase chemicals could be achieved via ambient proton transfer ionization, ion intensity was found to be stable with humidity ranged from ∼10% to ∼100%. - Highlights: • A humidity independent mass spectrometric method for gas phase samples analysis. • A universal and good sensitivity method. • The method can real time identify plant released raw chemicals. - Abstract: In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m{sup −3}, ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages.

  10. Gas phase infrared spectra and corresponding DFT calculations of α, ω-diphenylpolyenes

    Science.gov (United States)

    Biemann, Lars; Braun, Michaela; Kleinermanns, Karl

    2010-01-01

    We present gas phase Fourier Transform Infrared (FTIR) spectra of the homologue series of α, ω-diphenylpolyenes consisting of trans- and cis-stilbene, diphenylbutadiene (DPB) and diphenylhexatriene (DPH) obtained by a fast thermal heating technique that enables vaporization without decomposition. Infrared marker bands for the cis-isomers of the polyenes have been identified by density functional calculations at the B3LYP/TZVP level of theory. The all trans isomers of DPB and DPH do not interconvert to the cis-isomers in the gas phase at 200 °C.

  11. A Proposed Mechanism of Photocatalytic Oxidation of Trichloroethylene in Gas Phase

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    GC/MS has been used to identify gas phase products and intermediates formed during the gas phase photocatalytic oxidation of trichloroethylene (TCE) on TiO2 with low BET surface area.A new byproduct, oxalyl choloride (ClCOCOCl) was detected together with other byproducts such as COCl2, CHCl3, DCAC and C2HCl5.Firstly the method of perturbation on the reaction system was conducted.Very little amount of water was carried into the feed gas and subsequent changes were observed.The discussion based on the product distribution changes led to a postulated mechanism consisting of two stages.

  12. Direct monitoring of the liquid and gas phases during a fermentation in a computer-mass-spectrometer-fermentor system

    Energy Technology Data Exchange (ETDEWEB)

    Pungor, E. Jr.; Schaefer, E.J.; Cooney, C.L.; Weaver, J.C.

    1983-01-01

    Measurement of chemical concentrations is a weak link in the monitoring of fermentations. The use of a computer-controlled mass-spectrometer (MS) has made possible the measurement of one or more volatile compounds on an essentially continuous basis, both in the liquid (broth) and the gas (headspace) phases. For our purposes, the MS was used, not as a spectrometer for chemical identification, but as a programmable detector for measuring concentrations of different compounds. Specifically, a computer-controlled MS was employed during the fermentation of Saccharomyces italicus, to monitor N/sub 2/, O/sub 2/, and CO/sub 2/ concentration in the gas phase, and N/sub 2/, O/sub 2/, CO/sub 2/, and ethanol in the liquid phase. The performance of the MS was carefully analyzed.

  13. A microcomputer-controlled gas phase microreactor system

    Energy Technology Data Exchange (ETDEWEB)

    Morris, R.M.

    1983-08-01

    Although automated reactors are effective tools for studying a single type of reaction or optimizing catalyst performance, they may not be well suited for exploratory research. These reactors generally have several shortcomings. First, they may have limited versatility since they are usually designed with a single application in mind. Second, computer systems used for process control and data acquisition are often expensive and complex, so that once they are set up for a given application, it is quite difficult to adapt them for another. Because of these restrictions, experimental reactors are often operated manually, requiring a full-time operator to monitor operations and acquire data. This is a greater problem in laboratories where projects are often short-term, and the costs of setting up an automated reactor may outweigh the benefits of automation. For an automated reactor to be cost-effective in such an environment, both reactor hardware and control software must be versatile enough that they can be easily modified and adapted for different experiments. An automated gas-flow microreactor has been designed and constructed which is both inexpensive and flexible. The reactor is capable of performing three different types of experiments, 1) continuous reagent feed with analysis of the product stream, 2) pulsed-flow experiments, and 3) temperature-programmed desorption (TPD) and reaction (TPR). Conversion of the reactor from one configuration to another requires less than one hour. Process control and data acquisition are performed using an Apple II Plus microcomputer (Apple Computer Corp., Cupertino, Calif.) and an ISAAC interface device (Cyborg Corp., Newton, Mass.).

  14. Isopropyl alcohol tank installed at A-3 Test Stand

    Science.gov (United States)

    2009-01-01

    An isopropyl alcohol (IPA) tank is lifted into place at the A-3 Test Stand being built at NASA's John C. Stennis Space Center. Fourteen IPA, water and liquid oxygen (LOX) tanks are being installed to support the chemical steam generators to be used on the A-3 Test Stand. The IPA and LOX tanks will provide fuel for the generators. The water will allow the generators to produce steam that will be used to reduce pressure inside the stand's test cell diffuser, enabling operators to simulate altitudes up to 100,000 feet. In that way, operators can perform the tests needed on rocket engines being built to carry humans back to the moon and possibly beyond. The A-3 Test Stand is set for completion and activation in 2011.

  15. Time resolve study on isopropyl-ether porphyrindiol

    Institute of Scientific and Technical Information of China (English)

    ZHANG; Lianwen; (张连文); YAO; Side; (姚思德); LIN; Weizhen; (林维真); CHEN; Zhilong; (陈志龙)

    2003-01-01

    A novel fat-soluble porphyrin derivative--isopropyl-ether porphyrindiol (IPEP) has been investigated using the nanosecond laser photolysis and pulse radiolysis. In acetonitrile, IPEP-excited triplet state shows two relative absorption areas peaking at 320 and 430 nm, molar extinction coefficients by energytransfer method (in benzene solution) are proved to be ε(315) = 1.07×105, ε(450) = 3.3×104 L3@mol-1@cm-1 and the excited triplet state quantum yield by comparative method is 0.18. Laser photolysis of IPEP in dGMP-containing solutionshows that the triplet state cannot excite/oxidize dGMP via the energy/electrontransfer process.

  16. Gas-phase infrared multiple photon dissociation spectroscopy of isolated SF6- and SF5- anions

    NARCIS (Netherlands)

    Steill, J. D.; Oomens, J.; Eyler, J. R.; Compton, R. N.

    2008-01-01

    Resonantly enhanced multiple photon dissociation of gas-phase SF6- and SF5- is studied using tunable infrared light from the FELIX free electron laser. The photodissociation spectrum of the sulfur hexafluoride anion, producing SF5-, is recorded over the spectral range of 250-1650 cm(-1). The infrare

  17. Gas phase considerations for the growth of device quality nanocrystalline silicon at high rate

    NARCIS (Netherlands)

    Rath, J.K.; Verkerk, A.D.; Liu, Y.; Brinza, M.; Goedheer, W.J.; Schropp, R.E.I.

    2008-01-01

    In order to increase industrial viability and to find niche markets, high deposition rate and low temperature depositions compared to standard deposition conditions are two recent trends in research areas concerning thin film silicon. In situ diagnostic tools to monitor gas phase conditions are usef

  18. Gas phase considerations for the growth of device quality nanocrystalline silicon at high rate

    NARCIS (Netherlands)

    J.K. Rath,; Verkerk, A. D.; Liu, Y.; Brinza, M.; W. J. Goedheer,; Schropp, R. E. I.

    2009-01-01

    In order to increase industrial viability and to find niche markets, high deposition rate and low temperature depositions compared to standard deposition conditions are two recent trends in research areas concerning thin film silicon. In situ diagnostic tools to monitor gas phase conditions are usef

  19. Cationic and neutral nitrosamide: Viable molecules in the dilute gas phase

    DEFF Research Database (Denmark)

    Egsgaard, H.; Carlsen, L.; Weiske, T.;

    1992-01-01

    Nitrosamide, NH2NO, has been generated and characterized in the dilute gas phase by means of neutralization reionization mass spectrometry in combination with extensive isotopic labelling. The molecule was found to be stable under these conditions having a minimal lifetime in the microsecond time...

  20. Experimental Gas-Phase Thermochemistry for Alkane Reductive Elimination from Pt(IV)

    NARCIS (Netherlands)

    Couzijn, Erik P. A.; Kobylianskii, Ilia J.; Moret, Marc-Etienne; Chen, Peter

    2014-01-01

    The gas-phase reactivity of the [(NN)(PtMe3)-Me-IV](+) (NN = alpha-diimine) complex 1 and its acetonitrile adduct has been investigated by tandem mass spectrometry. The only observed reaction from the octahedral d(6) complex 1 center dot MeCN is the simple dissociation of the coordinated solvent mol

  1. Conformation Switching in Gas-Phase Complexes of Histidine with Alkaline Earth Ions

    NARCIS (Netherlands)

    Dunbar, R. C.; Hopkinson, A. C.; Oomens, J.; Siu, C. K.; Siu, K. W. M.; Steill, J. D.; Verkerk, U. H.; Zhao, J. F.

    2009-01-01

    Infrared multiple photon dissociation spectroscopy of gas-phase doubly charged alkaline earth complexes of histidine reveals a transition from dominance of the zwitterion (salt bridge, SB) conformation with Ba2+ to substantial presence of the canonical (charge-solvated, CS) conformation with Ca2+. T

  2. Zwitterionic states in gas-phase polypeptide ions revealed by 157-nm ultra-violet photodissociation

    DEFF Research Database (Denmark)

    Kjeldsen, Frank; Silivra, Oleg A; Zubarev, Roman A

    2006-01-01

    carboxylic groups relative to competing COOH losses (45 Da) from neutral carboxylic groups. Loss of CO2 is a strong indication of the presence of a zwitterionic [(+)...(-)...(+)] salt bridge in the gas-phase polypeptide cation. This method provides a tool for studying, for example, the nature of binding...

  3. Imaging Molecular Structure through Femtosecond Photoelectron Diffraction on Aligned and Oriented Gas-Phase Molecules

    DEFF Research Database (Denmark)

    Boll, Rebecca; Rouzee, Arnaud; Adolph, Marcus

    2014-01-01

    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray Free-Electron Laser. We present results of two experiments aimed at measuring photoelectron angular...

  4. DEMONSTRATION BULLETIN: GAS-PHASE CHEMICAL REDUCTION - ECO LOGIC INTERNATIONAL, INC.

    Science.gov (United States)

    The patented Eco Logic Process employs a gas-phase reduction reaction of hydrogen with organic and chlorinated organic compounds at elevated temperatures to convert aqueous and oily hazardous contaminants into a hydrocarbon-rich gas product. After passing through a scrubber, the ...

  5. ECO LOGIC INTERNATIONAL GAS-PHASE CHEMICAL REDUCTION PROCESS - THE THERMAL DESORPTION UNIT - APPLICATIONS ANALYSIS REPORT

    Science.gov (United States)

    ELI ECO Logic International, Inc.'s Thermal Desorption Unit (TDU) is specifically designed for use with Eco Logic's Gas Phase Chemical Reduction Process. The technology uses an externally heated bath of molten tin in a hydrogen atmosphere to desorb hazardous organic compounds fro...

  6. Experimental Gas-Phase Thermochemistry for Alkane Reductive Elimination from Pt(IV)

    NARCIS (Netherlands)

    Couzijn, Erik P. A.; Kobylianskii, Ilia J.; Moret, Marc-Etienne; Chen, Peter

    2014-01-01

    The gas-phase reactivity of the [(NN)(PtMe3)-Me-IV](+) (NN = alpha-diimine) complex 1 and its acetonitrile adduct has been investigated by tandem mass spectrometry. The only observed reaction from the octahedral d(6) complex 1 center dot MeCN is the simple dissociation of the coordinated solvent

  7. Structure analysis of large argon clusters from gas-phase electron diffraction data: some recent results

    NARCIS (Netherlands)

    Waal, van de B.W.

    1999-01-01

    An up-to-date overview of recent developments in the structure elucidation of large ArN-clusters (103gas-phase electron diffraction data, is given. Although a satisfactory model for N3000 had been found in 1996, the size range beyond N10,000 presents new and unexpected problems. T

  8. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction.

    Science.gov (United States)

    Zhu, Hongying; Huang, Guangming

    2015-03-31

    In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m(-3), ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages.

  9. Direct Numerical Simulation of biomass pyrolysis and combustion with gas phase reactions

    NARCIS (Netherlands)

    Aswasthi, A.; Kuerten, J.G.M.; Geurts, B.J.

    2016-01-01

    We present Direct Numerical Simulation of biomass pyrolysis and combustion in a turbulent channel flow. The model includes simplified models for biomass pyrolysis and char combustion along with a model for particle tracking. The gas phase is modelled as a mixture of reacting gas species. The gas-pa

  10. Bond-specific dissociation following excitation energy transfer for distance constraint determination in the gas phase.

    Science.gov (United States)

    Hendricks, Nathan G; Lareau, Nichole M; Stow, Sarah M; McLean, John A; Julian, Ryan R

    2014-09-24

    Herein, we report chemistry that enables excitation energy transfer (EET) to be accurately measured via action spectroscopy on gaseous ions in an ion trap. It is demonstrated that EET between tryptophan or tyrosine and a disulfide bond leads to excited state, homolytic fragmentation of the disulfide bond. This phenomenon exhibits a tight distance dependence, which is consistent with Dexter exchange transfer. The extent of fragmentation of the disulfide bond can be used to determine the distance between the chromophore and disulfide bond. The chemistry is well suited for the examination of protein structure in the gas phase because native amino acids can serve as the donor/acceptor moieties. Furthermore, both tyrosine and tryptophan exhibit unique action spectra, meaning that the identity of the donating chromophore can be easily determined in addition to the distance between donor/acceptor. Application of the method to the Trpcage miniprotein reveals distance constraints that are consistent with a native-like fold for the +2 charge state in the gas phase. This structure is stabilized by several salt bridges, which have also been observed to be important previously in proteins that retain native-like structures in the gas phase. The ability of this method to measure specific distance constraints, potentially at numerous positions if combined with site-directed mutagenesis, significantly enhances our ability to examine protein structure in the gas phase.

  11. Generation of naphthoquinone radical anions by electrospray ionization: solution, gas-phase, and computational chemistry studies.

    Science.gov (United States)

    Vessecchi, Ricardo; Naal, Zeki; Lopes, José N C; Galembeck, Sérgio E; Lopes, Norberto P

    2011-06-02

    Radical anions are present in several chemical processes, and understanding the reactivity of these species may be described by their thermodynamic properties. Over the last years, the formation of radical ions in the gas phase has been an important issue concerning electrospray ionization mass spectrometry studies. In this work, we report on the generation of radical anions of quinonoid compounds (Q) by electrospray ionization mass spectrometry. The balance between radical anion formation and the deprotonated molecule is also analyzed by influence of the experimental parameters (gas-phase acidity, electron affinity, and reduction potential) and solvent system employed. The gas-phase parameters for formation of radical species and deprotonated species were achieved on the basis of computational thermochemistry. The solution effects on the formation of radical anion (Q(•-)) and dianion (Q(2-)) were evaluated on the basis of cyclic voltammetry analysis and the reduction potentials compared with calculated electron affinities. The occurrence of unexpected ions [Q+15](-) was described as being a reaction between the solvent system and the radical anion, Q(•-). The gas-phase chemistry of the electrosprayed radical anions was obtained by collisional-induced dissociation and compared to the relative energy calculations. These results are important for understanding the formation and reactivity of radical anions and to establish their correlation with the reducing properties by electrospray ionization analyses.

  12. Analytical solutions for a soil vapor extraction model that incorporates gas phase dispersion and molecular diffusion

    Science.gov (United States)

    Huang, Junqi; Goltz, Mark N.

    2017-06-01

    To greatly simplify their solution, the equations describing radial advective/dispersive transport to an extraction well in a porous medium typically neglect molecular diffusion. While this simplification is appropriate to simulate transport in the saturated zone, it can result in significant errors when modeling gas phase transport in the vadose zone, as might be applied when simulating a soil vapor extraction (SVE) system to remediate vadose zone contamination. A new analytical solution for the equations describing radial gas phase transport of a sorbing contaminant to an extraction well is presented. The equations model advection, dispersion (including both mechanical dispersion and molecular diffusion), and rate-limited mass transfer of dissolved, separate phase, and sorbed contaminants into the gas phase. The model equations are analytically solved by using the Laplace transform with respect to time. The solutions are represented by confluent hypergeometric functions in the Laplace domain. The Laplace domain solutions are then evaluated using a numerical Laplace inversion algorithm. The solutions can be used to simulate the spatial distribution and the temporal evolution of contaminant concentrations during operation of a soil vapor extraction well. Results of model simulations show that the effect of gas phase molecular diffusion upon concentrations at the extraction well is relatively small, although the effect upon the distribution of concentrations in space is significant. This study provides a tool that can be useful in designing SVE remediation strategies, as well as verifying numerical models used to simulate SVE system performance.

  13. Why do disk galaxies present a common gas-phase metallicity gradient?

    Science.gov (United States)

    Chang, R.; Zhang, Shuhui; Shen, Shiyin; Yin, Jun; Hou, Jinliang

    2017-03-01

    CALIFA data show that isolated disk galaxies present a common gas-phase metallicity gradient, with a characteristic slope of -0.1dex/re between 0.3 and 2 disk effective radius re (Sanchez et al. 2014). Here we construct a simple model to investigate which processes regulate the formation and evolution.

  14. Alteration of gas phase ion polarizabilities upon hydration in high dielectric liquids.

    Science.gov (United States)

    Buyukdagli, Sahin; Ala-Nissila, T

    2013-07-28

    We investigate the modification of gas phase ion polarizabilities upon solvation in polar solvents and ionic liquids. To this aim, we develop a classical electrostatic theory of charged liquids composed of solvent molecules modeled as finite size dipoles, and embedding polarizable ions that consist of Drude oscillators. In qualitative agreement with ab initio calculations of polar solvents and ionic liquids, the hydration energy of a polarizable ion in both types of dielectric liquid is shown to favor the expansion of its electronic cloud. Namely, the ion carrying no dipole moment in the gas phase acquires a dipole moment in the liquid environment, but its electron cloud also reaches an enhanced rigidity. We find that the overall effect is an increase of the gas phase polarizability upon hydration. In the specific case of ionic liquids, it is shown that this hydration process is driven by a collective solvation mechanism where the dipole moment of a polarizable ion induced by its interaction with surrounding ions self-consistently adds to the polarization of the liquid, thereby amplifying the dielectric permittivity of the medium in a substantial way. We propose this self-consistent hydration as the underlying mechanism behind the high dielectric permittivities of ionic liquids composed of small charges with negligible gas phase dipole moment. Hydration being a correlation effect, the emerging picture indicates that electrostatic correlations cannot be neglected in polarizable liquids.

  15. Catalyst for the carboxylation of carbonylated compounds in the gas phase

    DEFF Research Database (Denmark)

    2013-01-01

    The invention relates to a catalyst for the carboxylation of carbonylated compounds in the gas phase. Said catalyst consists of a metal complex which is active when the carboxylation is under reaction conditions and an organic salt, which is solid under normal conditions and liquid under reaction...

  16. Numerical modeling of gas-phase kinetics in formation of secondary aerosol

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Three basic modules of gas-phase photochemical reactions involved in the formation of secondary aerosol are developed for modeling the concentration variation of precursors of aerosol, including ketone (RCOx), aldehyde (ALD), peroxyacetylnitrate (PAN), NO2, and SO2, followed by numerical solution for each of the modules. Reasonable trends of concentration variation of the precursors can be obtained from the proposed modules.

  17. Effect of Gas Phase Transport in Molten Carbonate Fuel Cell (I)

    Energy Technology Data Exchange (ETDEWEB)

    Lee, C.G.; Lim, H.C. [Korea Electric Power Research Institute, Taejon (Korea)

    1999-07-01

    The mass transfer effect in gas phase of molten carbonate fuel cell (MCFC) has not been profoundly studied. We have tried to investigate it with disturbance of reactant gas flow. An inert gas was added into anode and cathode reactant gas streams, and the resulting voltage shifts were analyzed. The disturbance of reactant gas was carried out at different reactant and inert gas flow rates, and current density. The results express that the anode performance is profoundly influenced by mass transfer in gas phase while the cathode is not. Moreover, the quantitative analysis of mass transfer effect in gas phase was available by means of the inert gas disturbance. The method led to the separate analyses of mass transfer effect in cell. The effects of mass transfer in gas channel and porous electrode regions were measured by changing gas channel depth and electrode thickness. It was found that mass transfer resistance in anode takes place mainly in porous electrode. Meanwhile the voltage shifts in cathode represented both gas and liquid phase mass transfer effect separately. It was also found that the mass transfer resistance in gas phase is insignificant in cathode compared with that in anode. The voltage shift values, which mean mass transfer resistance in liquid phase, depended on oxidant gas composition. It implies that the cathode reaction in MCFC would be an O{sub 2} and CO{sub 2} mixed diffusion control process. (author). 11 refs., 5 figs.

  18. Gas-phase conformations of small polyprolines and their fragment ions by IRMPD spectroscopy

    NARCIS (Netherlands)

    Martens, J.K.; Grzetic, J.; Berden, G.; Oomens, J.

    2015-01-01

    Infrared multiple-photon dissociation (IRMPD) spectroscopy has been used to examine the gas-phase conformations of a series of short protonated polyproline ions (Pro(3)-Pro(6)), their CID/IRMPD fragmentation pathways, and the associated fragment identities. Consistent with previous findings, and in

  19. Electrocatalytic phenomena in gas phase reactions in solid electrolyte electrochemical cells

    NARCIS (Netherlands)

    Gellings, P.J.; Koopmans, H.J.A.; Burggraaf, A.J.

    1988-01-01

    The recent literature on electrocatalysis and electrocatalytic phenomena occurring in gas phase reactions on solid, oxygen conducting electrolytes is reviewed. In this field there are a number of different subjects which are treated separately. These are: the use of electrochemical methods to study

  20. Formation of complex organic molecules in cold objects: the role of gas phase reactions

    CERN Document Server

    Balucani, Nadia; Taquet, Vianney

    2015-01-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm (>30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain surface and gas phase chemistry. We propose here a new model to form DME and MF with gas phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthetized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairy well the observations towards L1544. It also...

  1. Gas-Phase Oxidation of Aqueous Ethanol by Nanoparticle Vanadia/Anatase Catalysts

    DEFF Research Database (Denmark)

    Jørgensen, Betina; Kristensen, Steffen Buus; Kunov-Kruse, Andreas Jonas

    2009-01-01

    The gas-phase oxidation of aqueous ethanol with dioxygen has been examined with a new nanoparticle V2O5/TiO2 catalyst. Product selectivity could to a large extent be controlled by small alterations of reaction parameters, allowing production of acetaldehyde at a selectivity higher than 90%, near...

  2. Ab initio study of gas phase and water-assisted tautomerization of maleimide and formamide

    Indian Academy of Sciences (India)

    Susheel Kalia; Anju Sharma; B S Kaith

    2007-11-01

    Maleimide serves as an important starting material in the synthesis of drugs and enzyme inhibitors. In the present paper, knowing the importance of tautomerization in maleimide for its drug action, potential energy surface of maleimide is studied and its tautomerization has been discussed and compared with tautomerization of formamide. Gas phase tautomerization of maleimide requires large amount of energy (23.21 kcal/mol) in comparison to formamide (15.05 kcal/mol) at HF/6-31+G* level. Thus making the proton transfer reaction a difficult process in gas phase. Water molecule lowers the energy barrier of tautomerization thus facilitating the tautomerization of maleimide to 5-hydroxy-pyrrol-2-one. Water assisted tautomerization of maleimide requires 19.60 kcal/mol energy at HF/6-31+G* and 17.63 kcal/mol energy at B3LYP/6-31+G* level, a decrease of 3.61 and 5.96 kcal/mol over gas phase tautomerization. Whereas, tautomerization of formamide requires 14.16 and 12.84 kcal/mol energy, a decrease of 0.89 and 2.01 kcal/mol energy over gas phase tautomerization at HF/6-31+G* and B3LYP/6-31+G* level, respectively. Water-assisted tautomerization in maleimide and formamide showed that difference in energy barrier reduces to 2.83 kcal/mol from 10.41 kcal/mol (in gas phase) at B3LYP level, which resulted that maleimide readily undergoes tautomerization in water molecule.

  3. A cylindrical quadrupole ion trap in combination with an electrospray ion source for gas-phase luminescence and absorption spectroscopy

    Science.gov (United States)

    Stockett, Mark H.; Houmøller, Jørgen; Støchkel, Kristian; Svendsen, Annette; Brøndsted Nielsen, Steen

    2016-05-01

    A relatively simple setup for collection and detection of light emitted from isolated photo-excited molecular ions has been constructed. It benefits from a high collection efficiency of photons, which is accomplished by using a cylindrical ion trap where one end-cap electrode is a mesh grid combined with an aspheric condenser lens. The geometry permits nearly 10% of the emitted light to be collected and, after transmission losses, approximately 5% to be delivered to the entrance of a grating spectrometer equipped with a detector array. The high collection efficiency enables the use of pulsed tunable lasers with low repetition rates (e.g., 20 Hz) instead of continuous wave (cw) lasers or very high repetition rate (e.g., MHz) lasers that are typically used as light sources for gas-phase fluorescence experiments on molecular ions. A hole has been drilled in the cylinder electrode so that a light pulse can interact with the ion cloud in the center of the trap. Simulations indicate that these modifications to the trap do not significantly affect the storage capability and the overall shape of the ion cloud. The overlap between the ion cloud and the laser light is basically 100%, and experimentally >50% of negatively charged chromophore ions are routinely photodepleted. The performance of the setup is illustrated based on fluorescence spectra of several laser dyes, and the quality of these spectra is comparable to those reported by other groups. Finally, by replacing the optical system with a channeltron detector, we demonstrate that the setup can also be used for gas-phase action spectroscopy where either depletion or fragmentation is monitored to provide an indirect measurement on the absorption spectrum of the ion.

  4. The role of gas phase reactions in the deflagration-to-detonation transition of high energy propellants

    Science.gov (United States)

    Boggs, T. L.; Price, C. F.; Atwood, A. I.; Zurn, D. E.; Eisel, J. L.; Derr, R. L.

    1980-01-01

    The inadequacies of the two commonly used assumptions are shown, along with the need for considering gas phase reactions. Kinetic parameters that describe the gas phase reactions for several ingredients are provided, and the first steps in convective combustion leading to deflagration to detonation transition are described.

  5. MOLECULAR SPECTROSCPY AND REACTIONS OF ACTINIDES IN THE GAS PHASE AND CRYOGENIC MATRICES

    Energy Technology Data Exchange (ETDEWEB)

    Heaven, Michael C.; Gibson, John K.; Marcalo, Joaquim

    2009-02-01

    In this chapter we review the spectroscopic data for actinide molecules and the reaction dynamics for atomic and molecular actinides that have been examined in the gas phase or in inert cryogenic matrices. The motivation for this type of investigation is that physical properties and reactions can be studied in the absence of external perturbations (gas phase) or under minimally perturbing conditions (cryogenic matrices). This information can be compared directly with the results from high-level theoretical models. The interplay between experiment and theory is critically important for advancing our understanding of actinide chemistry. For example, elucidation of the role of the 5f electrons in bonding and reactivity can only be achieved through the application of experimentally verified theoretical models. Theoretical calculations for the actinides are challenging due the large numbers of electrons that must be treated explicitly and the presence of strong relativistic effects. This topic has been reviewed in depth in Chapter 17 of this series. One of the goals of the experimental work described in this chapter has been to provide benchmark data that can be used to evaluate both empirical and ab initio theoretical models. While gas-phase data are the most suitable for comparison with theoretical calculations, there are technical difficulties entailed in generating workable densities of gas-phase actinide molecules that have limited the range of species that have been characterized. Many of the compounds of interest are refractory, and problems associated with the use of high temperature vapors have complicated measurements of spectra, ionization energies, and reactions. One approach that has proved to be especially valuable in overcoming this difficulty has been the use of pulsed laser ablation to generate plumes of vapor from refractory actinide-containing materials. The vapor is entrained in an inert gas, which can be used to cool the actinide species to room

  6. Hydration energies of deprotonated amino acids from gas phase equilibria measurements.

    Science.gov (United States)

    Wincel, Henryk

    2008-08-01

    Singly hydrated clusters of deprotonated amino acids were studied using an electrospray high-pressure mass spectrometer equipped with a pulsed ion-beam reaction chamber. Thermochemical data, DeltaH(o), DeltaS(o), and DeltaG(o), for the hydration reaction [AA - H](-) + H(2)O = [AA - H](-).(H(2)O) were obtained from gas-phase equilibria determinations for AA = Gly, Ala, Val, Pro, Phe, Lys, Met, Trp, Gln, Arg, and Asp. The hydration free-energy changes are found to depend significantly on the side-chain substituents. The water binding energy in [AA - H](-).(H(2)O) increases with the gas-phase acidity of AA. The anionic hydrogen bond strengths in [AA - H](-).(H(2)O) are compared with those of the cationic bonds in the corresponding AAH(+).(H(2)O) systems.

  7. Simplification of the CBS-QB3 method for predicting gas-phase deprotonation free energies

    Science.gov (United States)

    Casasnovas, Rodrigo; Frau, Juan; Ortega-Castro, Joaquín; Salvà, Antoni; Donoso, Josefa; Muñoz, Francisco

    Simplified versions of CBS-QB3 model chemistry were used to calculate the free energies of 36 deprotonation reactions in the gas phase. The best such version, S9, excluded coupled cluster calculation [CCSD(T)], and empirical (ΔEemp) and spin-orbit (ΔEint) correction terms. The mean absolute deviation and root mean square thus obtained (viz. 1.24 and 1.56 kcal/mol, respectively) were very-close to those provided by the original CBS-QB3 method (1.19 and 1.52 kcal/mol, respectively). The high-accuracy of the proposed simplification and its computational expeditiousness make it an excellent choice for energy calculations on gas-phase deprotonation reactions in complex systems.

  8. Distinct Fragmentation Pathways of Anticancer Drugs Induced by Charge-Carrying Cations in the Gas Phase

    Science.gov (United States)

    Hong, Areum; Lee, Hong Hee; Heo, Chae Eun; Cho, Yunju; Kim, Sunghwan; Kang, Dukjin; Kim, Hugh I.

    2017-04-01

    With the growth of the pharmaceutical industry, structural elucidation of drugs and derivatives using tandem mass spectrometry (MS2) has become essential for drug development and pharmacokinetics studies because of its high sensitivity and low sample requirement. Thus, research seeking to understand fundamental relationships between fragmentation patterns and precursor ion structures in the gas phase has gained attention. In this study, we investigate the fragmentation of the widely used anticancer drugs, doxorubicin (DOX), vinblastine (VBL), and vinorelbine (VRL), complexed by a singly charged proton or alkali metal ion (Li+, Na+, K+) in the gas phase. The drug-cation complexes exhibit distinct fragmentation patterns in tandem mass spectra as a function of cation size. The trends in fragmentation patterns are explicable in terms of structures derived from ion mobility mass spectrometry (IM-MS) and theoretical calculations.

  9. Kinetic analysis of photocatalytic oxidation of gas-phase formaldehyde over titanium dioxide.

    Science.gov (United States)

    Liu, Hongmin; Lian, Zhiwei; Ye, Xiaojiang; Shangguan, Wenfeng

    2005-07-01

    Degradation of formaldehyde with different initial concentration over titanium dioxide was carried out in a photocatalytic reactor. Photocatalytic rates were well described by the simplified Langmuir-Hinshelwood model. The kinetic analysis shows that the apparent first-order reaction coefficient is lower and half-life of photocatalysis is longer for low concentration than for high concentration formaldehyde. A network formation model of the photocatalytic products was established. Experimental results and analysis demonstrate that carbon dioxide concentration and carbon monoxide concentration in gas phase vary exponentially with the illumination time and may be even higher than gas-phase formaldehyde concentration if there is much pre-adsorbed formaldehyde in adsorption equilibrium on catalysts before illumination. Carbon monoxide is found to be one of the by-products during formaldehyde photooxidation.

  10. Imaging molecular structure through femtosecond photoelectron diffraction on aligned and oriented gas-phase molecules.

    Science.gov (United States)

    Boll, Rebecca; Rouzée, Arnaud; Adolph, Marcus; Anielski, Denis; Aquila, Andrew; Bari, Sadia; Bomme, Cédric; Bostedt, Christoph; Bozek, John D; Chapman, Henry N; Christensen, Lauge; Coffee, Ryan; Coppola, Niccola; De, Sankar; Decleva, Piero; Epp, Sascha W; Erk, Benjamin; Filsinger, Frank; Foucar, Lutz; Gorkhover, Tais; Gumprecht, Lars; Hömke, André; Holmegaard, Lotte; Johnsson, Per; Kienitz, Jens S; Kierspel, Thomas; Krasniqi, Faton; Kühnel, Kai-Uwe; Maurer, Jochen; Messerschmidt, Marc; Moshammer, Robert; Müller, Nele L M; Rudek, Benedikt; Savelyev, Evgeny; Schlichting, Ilme; Schmidt, Carlo; Scholz, Frank; Schorb, Sebastian; Schulz, Joachim; Seltmann, Jörn; Stener, Mauro; Stern, Stephan; Techert, Simone; Thøgersen, Jan; Trippel, Sebastian; Viefhaus, Jens; Vrakking, Marc; Stapelfeldt, Henrik; Küpper, Jochen; Ullrich, Joachim; Rudenko, Artem; Rolles, Daniel

    2014-01-01

    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray free-electron laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C(8)H(5)F) and dissociating, laser-aligned 1,4-dibromobenzene (C(6)H(4)Br(2)) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments.

  11. Imaging Molecular Structure through Femtosecond Photoelectron Diffraction on Aligned and Oriented Gas-Phase Molecules

    CERN Document Server

    Boll, R; Adolph, M; Anielski, D; Aquila, A; Bari, S; Bomme, C; Bostedt, C; Bozek, J D; Chapman, H N; Christensen, L; Coffee, R; Coppola, N; De, S; Decleva, P; Epp, S W; Erk, B; Filsinger, F; Foucar, L; Gorkhover, T; Gumprecht, L; Hoemke, A; Holmegaard, L; Johnsson, P; Kienitz, J S; Kierspel, T; Krasniqi, F; Kuehnel, K -U; Maurer, J; Messerschmidt, M; Moshammer, R; Mueller, Nele L M; Rudek, B; Savelyev, E; Schlichting, I; Schmidt, C; Scholz, F; Schorb, S; Schulz, J; Seltmann, J; Stener, M; Stern, S; Techert, S; Thogersen, J; Trippel, S; Viefhaus, J; Vrakking, M; Stapelfeldt, H; Kuepper, J; Ullrich, J; Rudenko, A; Rolles, D

    2014-01-01

    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray Free-Electron Laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C8H5F) and dissociating, laseraligned 1,4-dibromobenzene (C6H4Br2) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments.

  12. Elusive Sulfurous Acid: Gas-Phase Basicity and IR Signature of the Protonated Species.

    Science.gov (United States)

    Sinha, Rajeev K; Scuderi, Debora; Maitre, Philippe; Chiavarino, Barbara; Crestoni, Maria Elisa; Fornarini, Simonetta

    2015-05-01

    The ion corresponding to protonated sulfurous acid, H3SO3(+), has been successfully delivered into the gas phase by electrospray ionization of the solution of a suitable precursor and an in-source fragmentation process. The neutral acid is a highly elusive molecule. However, its gas-phase basicity has been ascertained by means of a kinetic study of proton-transfer reactivity. The structure of the H3SO3(+) sampled ion has been probed by IRMPD spectroscopy in two complementary IR frequency ranges in conjunction with density functional theory calculations and found to conform to a trihydroxosulfonium ion. The characteristic IR signatures may aid in deciphering the presence of this species in extraterrestrial atmospheres.

  13. Infrared Action Spectroscopy of Low-Temperature Neutral Gas-Phase Molecules of Arbitrary Structure

    Science.gov (United States)

    Yatsyna, Vasyl; Bakker, Daniël J.; Salén, Peter; Feifel, Raimund; Rijs, Anouk M.; Zhaunerchyk, Vitali

    2016-09-01

    We demonstrate a technique for IR action spectroscopy that enables measuring IR spectra in a background-free fashion for low-temperature neutral gas-phase molecules of arbitrary structure. The method is exemplified experimentally for N -methylacetamide molecules in the mid-IR spectral range of 1000 - 1800 cm-1 , utilizing the free electron laser FELIX. The technique involves the resonant absorption of multiple mid-IR photons, which induces molecular dissociation. The dissociation products are probed with 10.49 eV vacuum ultraviolet photons and analyzed with a mass spectrometer. We also demonstrate the capability of this method to record, with unprecedented ease, mid-IR spectra for the molecular associates, such as clusters and oligomers, present in a molecular beam. In this way the mass-selected spectra of low-temperature gas-phase dimers and trimers of N -methylacetamide are measured in the full amide I-III range.

  14. Effect of duty-cycles on the air plasma gas-phase of dielectric barrier discharges

    Science.gov (United States)

    Barni, R.; Biganzoli, I.; Dell'Orto, E. C.; Riccardi, C.

    2015-10-01

    An experimental investigation concerning the effects of a duty-cycle in the supply of a dielectric barrier discharge in atmospheric pressure air has been performed. Electrical characteristics of the discharge have been measured, focusing mainly on the statistical properties of the current filaments and on dielectric surface charging, both affected by the frequent repetition of breakdown imposed by the duty-cycle. Information on the gas-phase composition was gathered too. In particular, a strong enhancement in the ozone formation rate is observed when suitable long pauses separate the active discharge phases. A simulation of the chemical kinetics in the gas-phase, based on a simplified discharge modeling, is briefly described in order to shed light on the observed increase in ozone production. The effect of a duty-cycle on surface modification of polymeric films in order to increase their wettability has been investigated too.

  15. Atmospheric Consequences of the Hydration in Gas Phase of Aldehydes and Ketones

    Science.gov (United States)

    Vaida, V.; Axson, J. L.; Maron, M. K.

    2010-12-01

    Aldehydes and ketones are known oxidation products of biogenic and anthropogenic VOCs and have been observed by field studies to be present in aerosol and cloud particles. While the gas-phase chemistry of these compounds is fairly well understood, their modeled concentration and role in SOA formation remains controversial. In aqueous solution aldehydes and ketones hydrate to form alcohols. We explore the hydration of these compounds in the gas phase and examine the water and photon mediated processes of these hydrates. The formation of hydrates can contribute to aerosol growth and formation by partitioning into clouds and aerosols because of their lower vapor pressure and tendency to form intermolecular hydrogen bonds. Hydration of aldehydes and ketones has important consequences to the atmospheric photochemistry of these organic compounds. The experimental approaches employ Fourier transform spectroscopy (FTS) and cavity ringdown spectroscopy (CRDS) to observe the formation of diols and hydrates by these molecules as a function of relative humidity.

  16. Gas-Phase Synthesis of 1-Silacyclopenta-2,4-diene.

    Science.gov (United States)

    Yang, Tao; Dangi, Beni B; Thomas, Aaron M; Sun, Bing-Jian; Chou, Tzu-Jung; Chang, Agnes H H; Kaiser, Ralf I

    2016-07-01

    Silole (1-silacyclopenta-2,4-diene) was synthesized for the first time by the bimolecular reaction of the simplest silicon-bearing radical, silylidyne (SiH), with 1,3-butadiene (C4 H6 ) in the gas phase under single-collision conditions. The absence of consecutive collisions of the primary reaction product prevents successive reactions of the silole by Diels-Alder dimerization, thus enabling the clean gas-phase synthesis of this hitherto elusive cyclic species from acyclic precursors in a single-collision event. Our method opens up a versatile and unconventional path to access a previously rather obscure class of organosilicon molecules (substituted siloles), which have been difficult to access through classical synthetic methods.

  17. (129) Xe and (131) Xe nuclear magnetic dipole moments from gas phase NMR spectra.

    Science.gov (United States)

    Makulski, Włodzimierz

    2015-04-01

    (3) He, (129) Xe and (131) Xe NMR measurements of resonance frequencies in the magnetic field B0=11.7586 T in different gas phase mixtures have been reported. Precise radiofrequency values were extrapolated to the zero gas pressure limit. These results combined with new quantum chemical values of helium and xenon nuclear magnetic shielding constants were used to determine new accurate nuclear magnetic moments of (129) Xe and (131) Xe in terms of that of the (3) He nucleus. They are as follows: μ((129) Xe) = -0.7779607(158)μN and μ((131) Xe) = +0.6918451(70)μN . By this means, the new 'helium method' for estimations of nuclear dipole moments was successfully tested. Gas phase NMR spectra demonstrate the weak intermolecular interactions observed on the (3) He and (129) Xe and (131) Xe shielding in the gaseous mixtures with Xe, CO2 and SF6 .

  18. Distinct Fragmentation Pathways of Anticancer Drugs Induced by Charge-Carrying Cations in the Gas Phase

    Science.gov (United States)

    Hong, Areum; Lee, Hong Hee; Heo, Chae Eun; Cho, Yunju; Kim, Sunghwan; Kang, Dukjin; Kim, Hugh I.

    2016-12-01

    With the growth of the pharmaceutical industry, structural elucidation of drugs and derivatives using tandem mass spectrometry (MS2) has become essential for drug development and pharmacokinetics studies because of its high sensitivity and low sample requirement. Thus, research seeking to understand fundamental relationships between fragmentation patterns and precursor ion structures in the gas phase has gained attention. In this study, we investigate the fragmentation of the widely used anticancer drugs, doxorubicin (DOX), vinblastine (VBL), and vinorelbine (VRL), complexed by a singly charged proton or alkali metal ion (Li+, Na+, K+) in the gas phase. The drug-cation complexes exhibit distinct fragmentation patterns in tandem mass spectra as a function of cation size. The trends in fragmentation patterns are explicable in terms of structures derived from ion mobility mass spectrometry (IM-MS) and theoretical calculations.

  19. Accumulation of polycyclic aromatic hydrocarbons by lichen transplants: Comparison with gas-phase passive air samplers.

    Science.gov (United States)

    Loppi, S; Pozo, K; Estellano, V H; Corsolini, S; Sardella, G; Paoli, L

    2015-09-01

    This study compared the accumulation of 16 polycyclic aromatic hydrocarbons (PAHs) in samples of the lichen Evernia prunastri exposed for 3 months in and around an industrial area of S Italy with that in co-located passive gas-phase air samplers. The results showed a strong linear correlations (R=0.96, P<0.05) between total PAHs in lichens and in passive samplers, clearly indicating that lichen transplants may provide direct quantitative information on the atmospheric load by total PAHs, allowing translation of lichen values into atmospheric concentrations. To the best of our knowledge this is the first study reporting such a correlation with gas-phase passive air samplers. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Ab initio treatment of gas phase GeO{sup 2+} doubly charged ion

    Energy Technology Data Exchange (ETDEWEB)

    Mogren Al Mogren, M. [Chemistry Department, Faculty of Science, King Saud University, PO Box 2455, Riyadh 11451 (Saudi Arabia); Ben Abdallah, D. [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications – LSAMA, Université de Tunis, Tunis (Tunisia); Department of General Studies, Riyadh Corporation of Technology, Technical and Vocational Training Corporation, PO Box 42826, Riyadh 11551 (Saudi Arabia); Hochlaf, M., E-mail: hochlaf@univ-mlv.fr [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)

    2015-01-13

    Highlights: • Theoretical investigation of the novel gas-phase molecular species GeO{sup 2+}. • Spectroscopic parameters of this dication in its electronic ground and exited states. • Theoretical double ionization spectrum of GeO. - Abstract: Using multi reference configuration interaction methodology in connection with a large basis set, we show that GeO{sup 2+} is a metastable species either in the ground or in the electronically excited states. This confirms the observation of this dication in gas phase by mass spectrometry. In addition, we derived a set of accurate spectroscopic terms for GeO{sup 2+} bound states. At the MRCI/aug-cc-pV5Z level of theory, the adiabatic double ionization energy of GeO is computed to be ∼28.93 eV.

  1. Liquid-gas phase transition in strange hadronic matter with relativistic models

    CERN Document Server

    Torres, James R; Menezes, Débora P

    2015-01-01

    Background: The advent of new dedicated experimental programs on hyperon physics is rapidly boosting the field, and the possibility of synthetizing multiple strange hypernuclei requires the addition of the strangeness degree of freedom to the models dedicated to nuclear structure and nuclear matter studies at low energy. Purpose: We want to settle the influence of strangeness on the nuclear liquid-gas phase transition. Because of the large uncertainties concerning the hyperon sector, we do not aim at a quantitative estimation of the phase diagram but rather at a qualitative description of the phenomenology, as model independent as possible. Method: We analyze the phase diagram of low density matter composed of neutrons, protons and $\\Lambda$ hyperons using a Relativistic Mean Field (RMF) model. We largely explore the parameter space to pin down generic features of the phase transition, and compare the results to ab-initio quantum Monte Carlo calculations. Results: We show that the liquid-gas phase transition ...

  2. Unusual hydroxyl migration in the fragmentation of β-alanine dication in the gas phase.

    Science.gov (United States)

    Piekarski, Dariusz Grzegorz; Delaunay, Rudy; Maclot, Sylvain; Adoui, Lamri; Martín, Fernando; Alcamí, Manuel; Huber, Bernd A; Rousseau, Patrick; Domaracka, Alicja; Díaz-Tendero, Sergio

    2015-07-14

    We present a combined experimental and theoretical study of the fragmentation of doubly positively charged β-alanine molecules in the gas phase. The dissociation of the produced dicationic molecules, induced by low-energy ion collisions, is analysed by coincidence mass spectrometric techniques; the coupling with ab initio molecular dynamics simulations allows rationalisation of the experimental observations. The present strategy gives deeper insights into the chemical mechanisms of multiply charged amino acids in the gas phase. In the case of the β-alanine dication, in addition to the expected Coulomb explosion and hydrogen migration processes, we have found evidence of hydroxyl-group migration, which leads to unusual fragmentation products, such as hydroxymethyl cation, and is necessary to explain some of the observed dominant channels.

  3. Molecular chain properties of poly(N-isopropyl acrylamide)

    Institute of Scientific and Technical Information of China (English)

    曾钫; 童真

    1999-01-01

    A series of poly( N-isopropyl acrylamide) (PNIPAM) samples with molecular weight ranging from 2.23×104 to 130×104 and molecular weight distribution Mw/Mn≤1.28 were obtained by free radical polymerization and repeat precipitation fractionation. The molecular weight Mw, second virial coefficient A2 as well as the mean-square-root radius of gyration 〈S2〉 for PNIPAM samples in tetrahydrofuran (THF) were determined by light scattering, and the relations were estimated at A2 ∞ Mw0.25) and 〈S2〉1/2=1.56×10-9 Mw0.56. The intrinsic viscosity for THF solution and methanol solution of PNIPAM samples was measured and the Mark-Houwink equations were obtained as [η]=6.90×10-5 M0/73 (THF solution) and [η]=1.07×10-4 M0.71 (methanol solution). The above results indicate that both THF and methanol are good solvents for PNIPAM. The limit characteristic ratio C∞ for PNIPAM in the two solutions was determined to be 10.6 by using Kurata-Stockmayer equation, indicating that the f

  4. Method and apparatus for selective capture of gas phase analytes using metal .beta.-diketonate polymers

    Science.gov (United States)

    Harvey, Scott D [Kennewick, WA

    2011-06-21

    A process and sensor device are disclosed that employ metal .beta.-diketonate polymers to selectively capture gas-phase explosives and weaponized chemical agents in a sampling area or volume. The metal .beta.-diketonate polymers can be applied to surfaces in various analytical formats for detection of: improvised explosive devices, unexploded ordinance, munitions hidden in cargo holds, explosives, and chemical weapons in public areas.

  5. Liquid-Gas Phase Transition for Asymmetric Nuclear Matter in the Zimanyi-Moszkowski Model

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xu-Ming; QIAN Wei-Liang; SU Ru-Keng

    2004-01-01

    By using the improved Zimanyi-Moszkowski (ZM) model including the freedom of nucleons, σ mesons, ω mesons and ρ mesons, we investigate the liquid-gas phase transition for asymmetric nuclear matter. It is found that the phase transition for asymmetric nuclear matter in the improved ZM model with the isospin vector ρ meson degree of freedom is well defined. The binodal surface, which is essential in the study of the phase transition process, is addressed.

  6. Organic molecules in ices and their release into the gas phase

    Science.gov (United States)

    Fayolle, Edith; Oberg, Karin I.; Garrod, Robin; van Dishoeck, Ewine; Rajappan, Mahesh; Bertin, Mathieu; Romanzin, Claire; Michaut, Xavier; Fillion, Jean-Hugues

    2015-08-01

    Organic molecules in the early stages of star formation are mainly produced in icy mantles surrounding interstellar dust grains. Identifying these complex organics and quantifying their abundance during the evolution of young stellar objects is of importance to understand the emergence of life. Simple molecules in ices, up to methanol in size, have been identified in the interstellar medium through their mid-IR vibrations, but band confusion prevents detections of more complex and less abundant organic molecules in interstellar ices. The presence of complex organics on grains can instead be indirectly inferred from observations of their rotational lines in the gas phase following ice sublimation.Thermal sublimation of protostellar ices occurs when icy grains flow toward a central protostar, resulting in the formation of a hot-core or a hot-corinos. The high degree of chemical complexity observed in these dense and warm regions can be the results of i) direct synthesis on the grains followed by desorption, but also to ii) the desorption of precursors from the ice followed by gas-phase chemistry. I will show how spatially resolved millimetric observations of hot cores and cooler protostellar environments, coupled to ice observations can help us pinpoint the ice or gas-phase origin of these organic species.Organic molecules have also recently been observed in cold environments where thermal desorption can be neglected. The presence of these cold molecules in the gas phase is most likely due to non-thermal desorption processes induced by, for e.g., photon-, electron-, cosmic-ray-irradiation, shock, exothermic reactions... I will present laboratory and observational efforts that push our current understanding of these non-thermal desorption processes and how they could be use to quantify the amount of organics in ices.

  7. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III ? gas phase reactions of inorganic halogens

    OpenAIRE

    Atkinson, R.; Baulch, D. L.; Cox, R A; J. N. Crowley; Hampson, R. F.; Hynes, R. G.; Jenkin, M. E.; M. J. Rossi; Troe, J.

    2007-01-01

    International audience; This article, the third in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of inorganic halogen species, which were last published in J. Phys. Chem. Ref. Data, in 2000 (Atkinson et al., 2000), were updated on the IUPAC website in 2003 and are updated again in the present evaluation. The article consists of a summary sheet...

  8. For Noble Gases, Energy is Positive for the Gas Phase, Negative for the Liquid Phase

    CERN Document Server

    Asanuma, Nobu-Hiko

    2016-01-01

    We found from experimental data that for noble gases and H$_2$, the energy is positive for the gas phase, and negative for the liquid, possibly except the small vicinity of the critical point, about $(1- T/T_c) \\le 0.005$. The line $E=E_c$, in the supercritical region is found to lie close to the Widom line, where $E_c$ is the critical energy.

  9. Diffuse Interstellar Bands: How Are They Related to Known Gas-Phase Constituents of the ISM?

    OpenAIRE

    Welty, Daniel E.

    2013-01-01

    In this brief review of recent work relating the DIBs to other gas-phase constituents of the ISM, we explore correlations between DIB equivalent widths and the column densities of various atomic and molecular species, drawn from a large database constructed for that purpose. The tightness and slopes of the correlations can provide information on how the DIBs might be related to those species (physically, chemically, spatially) and on various properties of the DIB carriers. Deviations from the...

  10. Non-conventional gas phase remediation of volatile halogenated compounds by dehydrated bacteria

    OpenAIRE

    Erable, Benjamin; Goubet, Isabelle; Seltana, Amira; Maugard, Thierry

    2009-01-01

    Traditional biological removal processes are limited by the low solubility of halogenated compounds in aqueous media. A new technology appears very suitable for the remediation of these volatile organic compounds (VOCs). Solid/gas bio-catalysis applied in VOC remediation can transform halogenated compounds directly in the gas phase using dehydrated cells as a bio-catalyst. The hydrolysis of volatile halogenated substrates into the corresponding alcohol was studied in a solid/gas bio...

  11. Noncovalent Halogen Bonding as a Mechanism for Gas-Phase Clustering

    Science.gov (United States)

    Wegeberg, Christina; Donald, William A.; McKenzie, Christine J.

    2017-10-01

    Gas-phase clustering of nonionizable iodylbenzene (PhIO2) is attributed to supramolecular halogen bonding. Electrospray ionization results in the formation of ions of proton-charged and preferably sodium-charged clusters assignable to [H(PhIO2) n ]+, n = 1-7; [Na(PhIO2) n ]+, n = 1-6; [Na2(PhIO2) n ]2+, n = 7-20; [HNa(PhIO2) n ]2+, n = 6-19; [HNa2(PhIO2) n ]3+, n = 15-30; and [Na3(PhIO2) n ]3+, n = 14-30. The largest cluster detected has a supramolecular mass of 7147 Da. Electronic structure calculations using the M06-2X functional with the 6-311++G(d,p) basis set for C, H, and O, and LANL2DZ basis set for I and Na predict 298 K binding enthalpies for the protonated and sodiated iodylbenzene dimers and trimers are greater than 180 kJ/mol. This is exceptionally high in comparison with other protonated and sodiated clusters with well-established binding enthalpies. Strongly halogen-bonded motifs found in the crystalline phases of PhIO2 and its derivatives serve as models for the structures of larger gas-phase clusters, and calculations on simple model gas-phase dimer and trimer clusters result in similar motifs. This is the first account of halogen bonding playing an extensive role in gas-phase associations. [Figure not available: see fulltext.

  12. Formation of complex organic molecules in cold objects: the role of gas phase reactions

    OpenAIRE

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-01-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm (>30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) ...

  13. GAS PHASE MOLECULAR DYNAMICS: HIGH-RESOLUTION SPECTROSCOPIC PROBES OF CHEMICAL DYNAMICS.

    Energy Technology Data Exchange (ETDEWEB)

    HALL, G.E.

    2006-05-30

    This research is carried out as part of the Gas Phase Molecular Dynamics group program in the Chemistry Department at Brookhaven National Laboratory. High-resolution spectroscopic tools are developed and applied to problems in chemical dynamics. Recent topics have included the state-resolved studies of collision-induced electronic energy transfer, dynamics of barrierless unimolecular reactions, and the kinetics and spectroscopy of transient species.

  14. Alteration of gas phase ion polarizabilities upon hydration in high dielectric liquids

    OpenAIRE

    2013-01-01

    We investigate the modification of gas phase ion polarizabilities upon solvation in polar solvents and ionic liquids. To this aim, we develop a classical electrostatic theory of charged liquids composed of solvent molecules modeled as finite size dipoles, and embedding polarizable ions that consist of Drude oscillators. In qualitative agreement with ab-initio calculations of polar solvents and ionic liquids, the hydration energy of a polarizable ion in both type of dielectric liquid is shown ...

  15. The partitioning of Nitric Acid between the gas phase and condensed phase of aqueous sulfate aerosols.

    Science.gov (United States)

    Mentel, T. F.; Folkers, M.; Sebald, H.; Wahner, A.

    2001-12-01

    The heterogeneous hydrolysis of N2O_5 on aqueous aerosol surfaces is an important source of atmospheric HNO3. We generated HNO3 by heterogeneous hydrolysis of N2O_5 on aqueous ammonium and sodium sulfate aerosols and studied its partitioning between the gas phase and the aerosol phase. The experiments were performed in the large aerosol chamber at the FZ-Jülich at several relative humidities. Gas phase processes and the composition of the aerosols were monitored on-line simultaneously by FTIR spectroscopy and by Steam Jet Aerosol Collection/Ion Chromatography. The aerosol size distributions in the range of 20 nm to 5 μ m were measured by differential electromobility classification and by aerodynamic particle sizing. In the presence of aqueous bisulfate and sulfate aerosols a fast heterogeneous formation HNO3 is observed. (The reaction probability of N2O_5 is about 0.02.) In the case of the acidic bisulfate aerosols the major fraction of heterogeneously formed HNO3 resides in the gas phase. For neutral sulfate aerosols a significant fraction of HNO3 is taken up by the condensed phase of the aerosols. This leads to a distinctive growth of the aerosol population during the heterogeneous hydrolysis of N2O_5, which is observable in the number size distribution as well as in IR extinction measurements. The observed partitioning of HNO3 between gas phase and aqueous aerosol phase can be quantitatively understood by a Pitzer based thermodynamic model for salt solutions of high ionic strength. The model calculations and low resolution FTIR spectroscopy demonstrate that protonation of sulfate to bisulfate is the driving force for the uptake of HNO3 in neutral sulfate aerosols.

  16. Solution Versus Gas-Phase Modification of Peptide Cations with NHS-Ester Reagents

    Science.gov (United States)

    Mentinova, Marija; Barefoot, Nathan Z.; McLuckey, Scott A.

    2012-02-01

    A comparison between solution and gas phase modification of primary amine sites in model peptide cations with N-hydroxysuccinimide (NHS) ester reagents is presented. In all peptides, the site of modification in solution was directed to the N-terminus by conducting reactions at pH = 5, whereas for the same peptides, a lysine residue was preferentially modified in the gas phase. The difference in pKa values of the N-terminus and ɛ-amino group of the lysine allows for a degree of control over sites of protonation of the peptides in aqueous solution. With removal of the dielectric and multiple charging of the peptide ions in the gas phase, the accommodation of excess charge can affect the preferred sites of reaction. Interaction of the lone pair of the primary nitrogen with a proton reduces its nucleophilicity and, as a result, its reactivity towards NHS-esters. While no evidence for reaction of the N-terminus with sulfo-NHS-acetate was noted in the model peptide cations, a charge inversion experiment using bis[sulfosuccinimidyl] suberate, a cross-linking reagent with two sulfo-NHS-ester functionalities, showed modification of the N-terminus. Hence, an unprotonated N-terminus can serve as a nucleophile to displace NHS, which suggests that its lack of reactivity with the peptide cations is likely due to the participation of the N-terminus in solvating excess charge.

  17. Amino Acids and Sugars in the Gas Phase: Microwave Data for Astrochemistry

    Science.gov (United States)

    Mata, S.; Cabezas, C.; Varela, M.; Peña, I.; Perez, C.; Blanco, S.; Sanz, M. E.; Lopez, J. C.; Alonso, J. L.

    2011-05-01

    Microwave spectroscopy, considered the most definitive gas phase structural probe, can distinguish between different conformational structures since they have unique spectroscopic constants and give separate rotational spectra. However it has been limited to molecular specimens having an appreciable vapor pressure. In general, molecules of biological importance have low vapor pressures and tend to undergo degradation upon heating. The combination of laser ablation with Fourier transform microwave spectroscopy in supersonic jets (LA-MB-FTMW) which overcomes the problems of thermal decomposition has rendered accessible the gas phase structural studies of these molecules. To date different α-, β- and γ-amino acids have been studied using this technique. Even in conformationally challenging systems the preferred conformations can be identified by rotational spectroscopy, as has been illustrated with the assignment of seven low-energy conformers in serine and threonine, six in cysteine and aspartic acid , and nine in γ-amino butyric (gaba). This technique has been successfully applied to the study of monosaccarides. Three conformers of the prototypes α-D-glucose and β-D-glucose have been characterized for the first time in the gas phase. After the first experimental observation of the monohydrated cluster of glycine, complexes between amino acids and nitrogen bases with water have also been investigated to obtain information on the changes induced in the conformational or tautomeric preferences by the addition of solvent molecules. The information given here is relevant for the unambiguous identification of these amino acids and sugars in the interstellar medium.

  18. All-gas-phase synthesis of UiO-66 through modulated atomic layer deposition

    Science.gov (United States)

    Lausund, Kristian Blindheim; Nilsen, Ola

    2016-01-01

    Thin films of stable metal-organic frameworks (MOFs) such as UiO-66 have enormous application potential, for instance in microelectronics. However, all-gas-phase deposition techniques are currently not available for such MOFs. We here report on thin-film deposition of the thermally and chemically stable UiO-66 in an all-gas-phase process by the aid of atomic layer deposition (ALD). Sequential reactions of ZrCl4 and 1,4-benzenedicarboxylic acid produce amorphous organic–inorganic hybrid films that are subsequently crystallized to the UiO-66 structure by treatment in acetic acid vapour. We also introduce a new approach to control the stoichiometry between metal clusters and organic linkers by modulation of the ALD growth with additional acetic acid pulses. An all-gas-phase synthesis technique for UiO-66 could enable implementations in microelectronics that are not compatible with solvothermal synthesis. Since this technique is ALD-based, it could also give enhanced thickness control and the possibility to coat irregular substrates with high aspect ratios. PMID:27876797

  19. All-gas-phase synthesis of UiO-66 through modulated atomic layer deposition

    Science.gov (United States)

    Lausund, Kristian Blindheim; Nilsen, Ola

    2016-11-01

    Thin films of stable metal-organic frameworks (MOFs) such as UiO-66 have enormous application potential, for instance in microelectronics. However, all-gas-phase deposition techniques are currently not available for such MOFs. We here report on thin-film deposition of the thermally and chemically stable UiO-66 in an all-gas-phase process by the aid of atomic layer deposition (ALD). Sequential reactions of ZrCl4 and 1,4-benzenedicarboxylic acid produce amorphous organic-inorganic hybrid films that are subsequently crystallized to the UiO-66 structure by treatment in acetic acid vapour. We also introduce a new approach to control the stoichiometry between metal clusters and organic linkers by modulation of the ALD growth with additional acetic acid pulses. An all-gas-phase synthesis technique for UiO-66 could enable implementations in microelectronics that are not compatible with solvothermal synthesis. Since this technique is ALD-based, it could also give enhanced thickness control and the possibility to coat irregular substrates with high aspect ratios.

  20. The Decomposition of Hydrazine in the Gas Phase and over an Iridium Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Michael W. [Ames Laboratory; Gordon, Mark S. [Ames Laboratory

    2013-09-30

    Hydrazine is an important rocket fuel, used as both a monopropellant and a bipropellant. This paper presents theoretical results to complement the extensive experimental studies of the gas phase and Ir catalyzed decompositions involved in the monopropellant applications of hydrazine. Gas phase electronic structure theory calculations that include electron correlation predict that numerous molecular and free radical reactions occur within the same energy range as the basic free radical pathways: NN bond breaking around 65 kcal/mol and NH bond breaking around 81 kcal/mol. The data suggest that a revision to existing kinetics modeling is desirable, based on the energetics and the new elementary steps reported herein. A supported Ir-6 octahedron model for the Shell 405 Iridium catalyst used in thrusters was developed. Self-Consistent Field and electron correlation calculations (with core potentials and associated basis sets) find a rich chemistry for hydrazine on this catalyst model. The model catalyst provides dramatically lower NN and NH bond cleavage energies and an even smaller barrier to breaking the NH bond by NH2 abstractions. Thus, the low temperature decomposition over the catalyst is interpreted in terms of consecutive NH2 abstractions to produce ammonia and nitrogen. The higher temperature channel, which has hydrogen and nitrogen products, may be due to a mixture of two mechanisms. These two mechanisms are successive NH cleavages with surface H + H recombinations, and the same type of assisted H-2 eliminations found to occur in the gas phase part of this study.

  1. Enantiomer-Selective Photo-Induced Reaction of Protonated Tryptophan with Disaccharides in the Gas Phase

    Science.gov (United States)

    Doan, Thuc N.; Fujihara, Akimasa

    2017-07-01

    In order to investigate chemical evolution in interstellar molecular clouds, enantiomer-selective photo-induced chemical reactions between an amino acid and disaccharides in the gas phase were examined using a tandem mass spectrometer containing an electrospray ionization source and a cold ion trap. Ultraviolet photodissociation mass spectra of cold gas-phase noncovalent complexes of protonated tryptophan (Trp) enantiomers with disaccharides consisting of two uc(d)-glucose units, such as uc(d)-maltose or uc(d)-cellobiose, were obtained by photoexcitation of the indole ring of Trp. NH2CHCOOH loss via cleavage of the Cα-Cβ bond in Trp induced by hydrogen atom transfer from the NH3 + group of a protonated Trp was observed in a noncovalent heterochiral H+(uc(l)-Trp)(uc(d)-maltose) complex. In contrast, a photo-induced chemical reaction forming the product ion with m/z 282 occurs in homochiral H+(uc(d)-Trp)(uc(d)-maltose). For uc(d)-cellobiose, both NH2CHCOOH elimination and the m/z 282 product ion were observed, and no enantiomer-selective phenomena occurred. The m/z 282 product ion indicates that the photo-induced C-glycosylation, which links uc(d)-glucose residues to the indole moiety of Trp via a C-C bond, can occur in cold gas-phase noncovalent complexes, and its enantiomer-selectivity depends on the structure of the disaccharide.

  2. Revision of the gas-phase acidity scale below 300 kcal mol(-1).

    Science.gov (United States)

    Leito, Ivo; Raamat, Elin; Kütt, Agnes; Saame, Jaan; Kipper, Karin; Koppel, Ilmar A; Koppel, Ivar; Zhang, Min; Mishima, Masaaki; Yagupolskii, Lev M; Garlyauskayte, Romute Yu; Filatov, Andrey A

    2009-07-23

    The gas-phase acidity (GA) scale from (CF(3)CO)(2)NH to (C(2)F(5)SO(2))(2)NH--about a 24 kcal mol(-1) range of gas-phase acidities--was reexamined using the Fourier transform ion cyclotron resonance equilibrium measurement approach. Some additions and modifications to the standard methodology of GA measurements were introduced (estimation of partial pressures from mass spectra of the compounds, instead of the pressure gauge readings and use of long reaction times) to achieve higher reliability. Gas-phase acidities of 18 compounds were determined for the first time. The results reveal a contraction of the previously published values in this part of the scale. In particular, the GA values of (CF(3)SO(2))(2)NH and (C(2)F(5)SO(2))(2)NH (important components of lithium ion battery electrolytes and ionic liquids) were revised toward stronger acidities from 291.8 kcal mol(-1) to 286.5 kcal mol(-1) and from 289.4 kcal mol(-1) to 283.7 kcal mol(-1) (i.e., by 5.3 and 5.7 kcal mol(-1)), respectively. Experimental and computational evidence is presented in support of the current results.

  3. Ion chemistry and gas-phase basicity of nickelocene by ion cyclotron resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Corderman, R.R.; Beauchamp, J.L.

    1976-01-01

    The gas-phase ion chemistry of bis(eta/sup 5/-cyclopentadienyl)nickel(nickelocene) is studied using the techniques of ion cyclotron resonance spectroscopy. Total rate constants for the reactions of the primary fragment ions at 70 eV are determined using trapped-ion methods. The long-lived nickelocene anion, Ni(C/sub 5/H/sub 5/)/sub 2//sup -/, is formed directly by electron attachment and is unreactive with a variety of simple molecules. Nickelocene is observed to be an exceptionally strong base in the gas phase. Equilibrium proton-transfer reactions are observed in mixtures of nickelocene with (CH/sub 3/)/sub 3/N and (C/sub 2/H/sub 5/)/sub 2/NH, from which the gas-phase basicity or proton affinity (PA) is determined to be 218.9 +- 1.0 kcal/mol relative to PA(NH/sub 3/) = 201 +- 1 kcal/mol. Attempts to determine the site of protonation were inconclusive. The ion chemistry and base strength of nickelocene and ferrocene are compared. 39 references, 2 figures, 3 tables.

  4. Ion chemistry and gas-phase basicity of nickelocene by ion cyclotron resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Corderman, R.D.; Beauchamp, J.L.

    1976-03-01

    The gas-phase ion chemistry of bis(eta/sup 5/-cyclopentadienyl)nickel (nickelocene) is studied using the techniques of ion cyclotron resonance spectroscopy. Total rate constants for the reactions of the primary fragment ions at 70 eV are determined using trapped-ion methods. The long-lived nickelocene anion, Ni(C/sub 5/H/sub 5/)/sub 2//sup -/, is formed directly by electron attachment and is unreactive with a variety of simple molecules. Nickelocene is observed to be an exceptionally strong base in the gas phase. Equilibrium proton-transfer reactions are observed in mixtures of nickelocene with (CH/sub 3/)/sub 3/N and (C/sub 2/H/sub 5/)/sub 2/NH, from which the gas-phase basicity or proton affinity (PA) is determined to be 218.9 +- 1.0 kcal/mol relative to PA(NH/sub 3/) = 201 +- 1 kcal/mol. Attempts to determine the site of protonation were inconclusive. The ion chemistry and base strength of nickelocene and ferrocene are compared. (auth)

  5. Gas-phase advanced oxidation as an integrated air pollution control technique

    Directory of Open Access Journals (Sweden)

    Getachew A. Adnew

    2016-03-01

    Full Text Available Gas-phase advanced oxidation (GPAO is an emerging air cleaning technology based on the natural self-cleaning processes that occur in the Earth’s atmosphere. The technology uses ozone, UV-C lamps and water vapor to generate gas-phase hydroxyl radicals that initiate oxidation of a wide range of pollutants. In this study four types of GPAO systems are presented: a laboratory scale prototype, a shipping container prototype, a modular prototype, and commercial scale GPAO installations. The GPAO systems treat volatile organic compounds, reduced sulfur compounds, amines, ozone, nitrogen oxides, particles and odor. While the method covers a wide range of pollutants, effective treatment becomes difficult when temperature is outside the range of 0 to 80 °C, for anoxic gas streams and for pollution loads exceeding ca. 1000 ppm. Air residence time in the system and the rate of reaction of a given pollutant with hydroxyl radicals determine the removal efficiency of GPAO. For gas phase compounds and odors including VOCs (e.g. C6H6 and C3H8 and reduced sulfur compounds (e.g. H2S and CH3SH, removal efficiencies exceed 80%. The method is energy efficient relative to many established technologies and is applicable to pollutants emitted from diverse sources including food processing, foundries, water treatment, biofuel generation, and petrochemical industries.

  6. Gas-phase self-assembly of uniform silica nanostructures decorated and doped with silver nanoparticles

    Science.gov (United States)

    Lai, Chao-Shun; Chen, Yi-Chen; Wang, Hsiao-Fang; Ho, Hsin-Chia; Ho, Rong-Ming; Tsai, De-Hao

    2017-01-01

    We report a systematic study of the controlled gas-phase synthesis of silver-silica hybrid nanostructures (Ag-SiO2 NP) using the concept of evaporation-induced self-assembly. The approach includes the use of a direct gas-phase electrophoresis for size classification and in situ characterization of mobility size. Transmission electron microscopy and ultraviolet-visible light spectroscopy were employed complementarily to determine the morphology and surface plasmon resonance of Ag-SiO2 NP. Results show that two types of Ag-SiO2 NPs were successfully synthesized: (1) AgNPs decorated on a SiO2-NP (Ag-T-SiO2 NP), and (2) AgNPs doped in a cluster of SiO2-NPs (Ag-C-SiO2 NP). The physical size, morphology, and compositions of Ag-SiO2 NPs were tunable through the adjustments of precursor concentrations and the selected mobility sizes. The results also show that SPR performance, colloidal stability, and dispersibility of AgNPs enhanced significantly in an aqueous environment after the hybridization with SiO2-NP (especially for Ag-C-SiO2 NP). The results and corresponding methodology summarized here provide the proof of concept to fabricate high-purity AgNP-based hybrid nanostructures through gas-phase evaporation-induced self-assembly for future biomedical applications (e.g., hyperthermal therapy, targeted drug delivery, and antibacterial applications).

  7. Thermodynamic analysis of fuels in gas phase: ethanol, gasoline and ethanol - gasoline predicted by DFT method.

    Science.gov (United States)

    Neto, A F G; Lopes, F S; Carvalho, E V; Huda, M N; Neto, A M J C; Machado, N T

    2015-10-01

    This paper presents a theoretical study using density functional theory to calculate thermodynamics properties of major molecules compounds at gas phase of fuels like gasoline, ethanol, and gasoline-ethanol mixture in thermal equilibrium on temperature range up to 1500 K. We simulated a composition of gasoline mixture with ethanol for a thorough study of thermal energy, enthalpy, Gibbs free energy, entropy, heat capacity at constant pressure with respect to temperature in order to study the influence caused by ethanol as an additive to gasoline. We used semi-empirical computational methods as well in order to know the efficiency of other methods to simulate fuels through this methodology. In addition, the ethanol influence through the changes in percentage fractions of chemical energy released in combustion reaction and the variations on thermal properties for autoignition temperatures of fuels was analyzed. We verified how ethanol reduces the chemical energy released by gasoline combustion and how at low temperatures the gas phase fuels in thermal equilibrium have similar thermodynamic behavior. Theoretical results were compared with experimental data, when available, and showed agreement. Graphical Abstract Thermodynamic analysis of fuels in gas phase.

  8. Direct Numerical Simulation of biomass pyrolysis and combustion with gas phase reactions

    Science.gov (United States)

    Awasthi, A.; Kuerten, J. G. M.; Geurts, B. J.

    2016-09-01

    We present Direct Numerical Simulation of biomass pyrolysis and combustion in a turbulent channel flow. The model includes simplified models for biomass pyrolysis and char combustion along with a model for particle tracking. The gas phase is modelled as a mixture of reacting gas species. The gas-particle interactions for mass, momentum, and energy exchange are included by two-way coupling terms. The effect of two-way coupling on the conversion time of biomass particles is found noticeable for particle volume fractions > 10-5. We also observe that at constant volume fraction the effect of two-way coupling increases as the particle size is reduced, due to the higher total heat exchange area in case of smaller particles. The inclusion of gas phase homogeneous reactions in the DNS model decreases the biomass pyrolysis time due to higher gas temperatures. In contrast, including gas phase reactions increases the combustion time of biomass due to the lower concentration of oxygen at the particle surface.

  9. Theoretical insight into the conversion of xylose to furfural in the gas phase and water.

    Science.gov (United States)

    Wang, Meng; Liu, Chao; Li, Qibin; Xu, Xiaoxiao

    2015-11-01

    Furfural (FF) is a valuable ring-containing organic compound in the decomposition of xylose and can be produced massively in hydrothermal condition. In this study, density functional theory (DFT) methods are employed to investigate the formation mechanism of FF from xylose and the solvent effects on FF formation. Kinetic and thermodynamic analyses indicate that xylulose could be the intermediate that leads to the formation of FF in the gas phase and water. The formation of xylulose is initiated by a six-membered transition state with energy barriers of 163.6 and 150.8 kJ mol(-1) in the gas phase and water, respectively. It is found that the strong stabilization of the reactants and transition states and the overall energy barriers of formation pathways of FF are reduced in water. The formation of FF is more thermodynamically favored in water compared with that in the gas phase. In addition, the inclusion of an explicit water molecule transforms four-membered transition states of ring-opening reaction, hydrogenation-cyclization, and dehydrations into less distorted six-membered transition states, which leads to the significant reduction of reaction barriers of FF formation.

  10. Improved machine learning method for analysis of gas phase chemistry of peptides

    Directory of Open Access Journals (Sweden)

    Ahn Natalie

    2008-12-01

    Full Text Available Abstract Background Accurate peptide identification is important to high-throughput proteomics analyses that use mass spectrometry. Search programs compare fragmentation spectra (MS/MS of peptides from complex digests with theoretically derived spectra from a database of protein sequences. Improved discrimination is achieved with theoretical spectra that are based on simulating gas phase chemistry of the peptides, but the limited understanding of those processes affects the accuracy of predictions from theoretical spectra. Results We employed a robust data mining strategy using new feature annotation functions of MAE software, which revealed under-prediction of the frequency of occurrence in fragmentation of the second peptide bond. We applied methods of exploratory data analysis to pre-process the information in the MS/MS spectra, including data normalization and attribute selection, to reduce the attributes to a smaller, less correlated set for machine learning studies. We then compared our rule building machine learning program, DataSqueezer, with commonly used association rules and decision tree algorithms. All used machine learning algorithms produced similar results that were consistent with expected properties for a second gas phase mechanism at the second peptide bond. Conclusion The results provide compelling evidence that we have identified underlying chemical properties in the data that suggest the existence of an additional gas phase mechanism for the second peptide bond. Thus, the methods described in this study provide a valuable approach for analyses of this kind in the future.

  11. Oxidative potential of gas phase combustion emissions - An underestimated and potentially harmful component of air pollution from combustion processes

    Science.gov (United States)

    Stevanovic, S.; Vaughan, A.; Hedayat, F.; Salimi, F.; Rahman, M. M.; Zare, A.; Brown, R. A.; Brown, R. J.; Wang, H.; Zhang, Z.; Wang, X.; Bottle, S. E.; Yang, I. A.; Ristovski, Z. D.

    2017-06-01

    The oxidative potential (OP) of the gas phase is an important and neglected aspect of environmental toxicity. Whilst prolonged exposure to particulate matter (PM) associated reactive oxygen species (ROS) have been shown to lead to negative health effects, the potential for compounds in gas phase to cause similar effects is yet to be understood. In this study we describe: the significance of the gas phase OP generated through vehicle emissions; discuss the origin and evolution of species contributing to measured OP; and report on the impact of gas phase OP on human lung cells. The model aerosol for this study was exhaust emitted from a Euro III Common-rail diesel engine fuelled with different blends of diesel and biodiesel. The gas phase of these emissions was found to be potentially as hazardous as the particle phase. Fuel oxygen content was found to negatively correlate with the gas phase OP, and positively correlate with particle phase OP. This signifies a complex interaction between reactive species present in gas and particle phase. Furthermore, this interaction has an overarching effect on the OP of both particle and gas phase, and therefore the toxicity of combustion emissions.

  12. Cleanroom airborne particulate limits and 70% isopropyl alcohol: a lingering problem for pharmaceutical manufacturing?

    Science.gov (United States)

    Eaton, Tim

    2009-01-01

    Seventy percent isopropyl alcohol (70% IPA) in water for injection is extensively utilised within pharmaceutical cleanrooms for glove and surface disinfection. When supplied in pressurised containers and delivered as an aerosol, it has been demonstrated that large quantities of 70% IPA particles are generated that remain airborne for substantial periods of time. Within non-unidirectional airflow cleanroom areas, such particles are likely to be recorded by the particle monitoring system. Consequently, the derived operational limits for particles will almost certainly be at "artificially high" levels and any particle generating activities with contamination potential may be masked. These high particle levels may not comply with the requirements of Annex 1 of the European Unions Guide to Good Manufacturing Practices (EU GGMP) and the United States Food and Drug Administration (FDA) Aseptic Processing Guideline. This is the case predominantly for the larger particles (> or =5 microm), the monitoring of which is exclusively required by the Annex 1 guide. However, by using canisters that deliver the 70% IPA as a stream, large quantities of particles are not generated and more meaningful and compliant operational levels can be obtained. Additionally, the EU GGMP's Annex 1 continuing requirement to monitor particles > or =5 microm appears to have little value or scientific justification and restricts further harmonisation of the European guide with the US FDA Aseptic Processing Guideline.

  13. Probing the Gas-Phase Dynamics of Graphene Chemical Vapour Deposition using in-situ UV Absorption Spectroscopy

    DEFF Research Database (Denmark)

    Shivayogimath, Abhay; Mackenzie, David; Luo, Birong

    2017-01-01

    of multilayer nucleation when backstreaming is suppressed. These results point to an important and previously undescribed mechanism for multilayer nucleation, wherein higher-order gas-phase carbon species play an integral role. Our work highlights the importance of gas-phase dynamics in understanding......The processes governing multilayer nucleation in the chemical vapour deposition (CVD) of graphene are important for obtaining high-quality monolayer sheets, but remain poorly understood. Here we show that higher-order carbon species in the gas-phase play a major role in multilayer nucleation...

  14. MOLECULAR SPECTROSCPY AND REACTIONS OF ACTINIDES IN THE GAS PHASE AND CRYOGENIC MATRICES

    Energy Technology Data Exchange (ETDEWEB)

    Heaven, Michael C.; Gibson, John K.; Marcalo, Joaquim

    2009-02-01

    In this chapter we review the spectroscopic data for actinide molecules and the reaction dynamics for atomic and molecular actinides that have been examined in the gas phase or in inert cryogenic matrices. The motivation for this type of investigation is that physical properties and reactions can be studied in the absence of external perturbations (gas phase) or under minimally perturbing conditions (cryogenic matrices). This information can be compared directly with the results from high-level theoretical models. The interplay between experiment and theory is critically important for advancing our understanding of actinide chemistry. For example, elucidation of the role of the 5f electrons in bonding and reactivity can only be achieved through the application of experimentally verified theoretical models. Theoretical calculations for the actinides are challenging due the large numbers of electrons that must be treated explicitly and the presence of strong relativistic effects. This topic has been reviewed in depth in Chapter 17 of this series. One of the goals of the experimental work described in this chapter has been to provide benchmark data that can be used to evaluate both empirical and ab initio theoretical models. While gas-phase data are the most suitable for comparison with theoretical calculations, there are technical difficulties entailed in generating workable densities of gas-phase actinide molecules that have limited the range of species that have been characterized. Many of the compounds of interest are refractory, and problems associated with the use of high temperature vapors have complicated measurements of spectra, ionization energies, and reactions. One approach that has proved to be especially valuable in overcoming this difficulty has been the use of pulsed laser ablation to generate plumes of vapor from refractory actinide-containing materials. The vapor is entrained in an inert gas, which can be used to cool the actinide species to room

  15. Evolution of Instrumentation for the Study of Gas-Phase Ion/Ion Chemistry via Mass Spectrometry

    OpenAIRE

    Xia, Yu; McLuckey, Scott A.

    2007-01-01

    The scope of gas phase ion/ion chemistry accessible to mass spectrometry is largely defined by the available tools. Due to the development of novel instrumentation, a wide range of reaction phenomenologies have been noted, many of which have been studied extensively and exploited for analytical applications. This perspective presents the development of mass spectrometry-based instrumentation for the study of the gas phase ion/ion chemistry in which at least one of the reactants is multiply-ch...

  16. Assessment of cytotoxicity of (N-isopropyl acrylamide) and Poly(N-isopropyl acrylamide)-coated surfaces

    Science.gov (United States)

    Cooperstein, Marta A; Canavan, Heather E

    2013-01-01

    Poly(N-isopropyl acrylamide) (pNIPAM) is one of the most popular stimulus-responsive polymers for research. It is especially of great interest in the field of tissue engineering. While it is known that the NIPAM monomer is toxic, there is little conclusive research on the cytotoxicity of the polymer. In this work, the relative biocompatibility of the NIPAM monomer, pNIPAM, and pNIPAM-coated substrates prepared using different polymerization (free radical and plasma polymerization) and deposition (spin coating and plasma polymerization) techniques was evaluated using appropriate cytotoxicity tests (MTS, Live/Dead, plating efficiency). Four different mammalian cell types (endothelial, epithelial, smooth muscle, and fibroblasts) were used for the cytotoxicity testing. The pNIPAM-coated surfaces were evaluated for their thermoresponse and surface chemistry using X-ray photoelectron spectroscopy and goniometry. We found that while cell viability on pNIPAM surfaces decreases when compared to controls, the viability also seems to be deposition type dependent, with sol–gel based pNIPAM surfaces being the least biocompatible. Long term experiments proved that all pNIPAM-coated surfaces were not cytotoxic to the four cell types evaluated in a direct contact test. Plating efficiency experiments did not show cytotoxicity. Cellular sensitivity to pNIPAM and to the NIPAM monomer varied depending on cell type. Endothelial cells consistently showed decreased viability after 48 hours of exposure to pNIPAM extracts and were more sensitive than the other cell lines to impurities in the polymer. PMID:24706136

  17. The gas phase origin of complex organic molecules precursors in prestellar cores

    Science.gov (United States)

    Bacmann, A.; Faure, A.

    2016-05-01

    Complex organic molecules (COMs) have long been observed in the warm regions surrounding nascent protostars. The recent discovery of oxygen-bearing COMs like methyl formate or dimethyl ether in prestellar cores (Bacmann et al. [2]), where gas and dust temperatures rarely exceed 10-15 K, has challenged the previously accepted models according to which COM formation relied on the diffusion of heavy radicals on warm (˜30 K) grains. Following these detections, new questions have arisen: do non-thermal processes play a role in increasing radical mobility or should new gas-phase routes be explored? The radicals involved in the formation of the aforementioned COMs, HCO and CH3O represent intermediate species in the grain-surface synthesis of methanol which proceeds via successive hydrogenations of CO molecules in the ice. We present here observations of methanol and its grain-surface precursors HCO, H2CO, CH3O in a sample of prestellar cores and derive their relative abundances. We find that the relative abundances HCO:H2CO:CH3O:CH3OH are constant across the core sample, close to 10:100:1:100. Our results also show that the amounts of HCO and CH3O are consistent with a gas-phase synthesis of these species from H2CO and CH3OH via radical-neutral or ion-molecule reactions followed by dissociative recombinations. Thus, while grain chemistry is necessary to explain the abundances of the parent volatile CH3OH, and possibly H2CO, the reactive species HCO and CH3O might be daughter molecules directly produced in the gas-phase.

  18. Gas-phase acid-base properties of melamine and cyanuric acid.

    Science.gov (United States)

    Mukherjee, Sumit; Ren, Jianhua

    2010-10-01

    The thermochemical properties of melamine and cyanuric acid were characterized using mass spectrometry measurements along with computational studies. A triple-quadrupole mass spectrometer was employed with the application of the extended Cooks kinetic method. The proton affinity (PA), gas-phase basicity (GB), and protonation entropy (Δ(p)S) of melamine were determined to be 226.2 ± 2.0 kcal/mol, 218.4 ± 2.0 kcal/mol, and 26.2 ± 2.0 cal/mol K, respectively. The deprotonation enthalpy (Δ(acid)H), gas-phase acidity (Δ(acid)G), and deprotonation entropy (Δ(acid)S) of cyanuric acid were determined to be 330.7 ± 2.0 kcal/mol, 322.9 ± 2.0 kcal/mol, and 26.1 ± 2.0 cal/mol K, respectively. The geometries and energetics of melamine, cyanuric acid, and related ionic species were calculated at the B3LYP/6-31+G(d) level of theory. The computationally predicted proton affinity of melamine (225.9 kcal/mol) and gas-phase deprotonation enthalpy of cyanuric acid (328.4 kcal/mol) agree well with the experimental results. Melamine is best represented as the imide-like triazine-triamine form and the triazine nitrogen is more basic than the amino group nitrogen. Cyanuric acid is best represented as the keto-like tautomer and the N-H group is the most probable proton donor.

  19. Gas-phase simulated moving bed: Propane/propylene separation on 13X zeolite.

    Science.gov (United States)

    Martins, Vanessa F D; Ribeiro, Ana M; Plaza, Marta G; Santos, João C; Loureiro, José M; Ferreira, Alexandre F P; Rodrigues, Alírio E

    2015-12-04

    In the last years several studies were carried out in order to separate gas mixtures by SMB technology; however, this technology has never been implemented on an industrial scale. In the present work, a gas phase SMB bench unit was built and tested for the separation of propane and propylene mixtures, using 13X zeolite extrudates as adsorbent and isobutane as desorbent. Three experiments were performed to separate propane/propylene by gas phase SMB in the bench scale unit with a 4-2-2 configuration, i.e., open loop circuit by suppressing section IV (desorbent regeneration followed by a recycle). Consequently, all the experiments were conducted using an external supply of pure isobutane as desorbent. Parameters such as switching time, extract and raffinate stream flow rates were changed to improve the efficiency of the process. Experimental results have shown that it is feasible to separate propylene from propane by gas phase SMB at a bench scale and that this process is a potential candidate to replace the conventional technologies for the propane/propylene separation. The performance parameters obtained are very promising for future development of this technology, since propylene was obtained in the extract stream with a purity of 99.93%, a recovery of 99.51%, and a productivity of [Formula: see text] . Propane was obtained in the raffinate stream with a purity of 98.10%, a recovery of 99.73% and a productivity of [Formula: see text] . The success of the above mentioned bench scale tests is a big step for the future implementation of this technology in a larger scale. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Enhanced Lipidome Coverage in Shotgun Analyses by using Gas-Phase Fractionation

    Science.gov (United States)

    Nazari, Milad; Muddiman, David C.

    2016-08-01

    A high resolving power shotgun lipidomics strategy using gas-phase fractionation and data-dependent acquisition (DDA) was applied toward comprehensive characterization of lipids in a hen ovarian tissue in an untargeted fashion. Using this approach, a total of 822 unique lipids across a diverse range of lipid categories and classes were identified based on their MS/MS fragmentation patterns. Classes of glycerophospholipids and glycerolipids, such as glycerophosphocholines (PC), glycerophosphoethanolamines (PE), and triglycerides (TG), are often the most abundant peaks observed in shotgun lipidomics analyses. These ions suppress the signal from low abundance ions and hinder the chances of characterizing low abundant lipids when DDA is used. These issues were circumvented by utilizing gas-phase fractionation, where DDA was performed on narrow m/z ranges instead of a broad m/z range. Employing gas-phase fractionation resulted in an increase in sensitivity by more than an order of magnitude in both positive- and negative-ion modes. Furthermore, the enhanced sensitivity increased the number of lipids identified by a factor of ≈4, and facilitated identification of low abundant lipids from classes such as cardiolipins that are often difficult to observe in untargeted shotgun analyses and require sample-specific preparation steps prior to analysis. This method serves as a resource for comprehensive profiling of lipids from many different categories and classes in an untargeted manner, as well as for targeted and quantitative analyses of individual lipids. Furthermore, this comprehensive analysis of the lipidome can serve as a species- and tissue-specific database for confident identification of other MS-based datasets, such as mass spectrometry imaging.

  1. Exploring the gas-phase spectroscopy of interstellar PAH and dust analogs: Astrophysical applications

    Science.gov (United States)

    Biennier, Ludovic; Salama, Farid; Allamandola, Lou; Gupta, Manish; O'Keefe, Anthony; Scherer, James J.

    We present and discuss the gas-phase electronic absorption spectra of selected ionized polycyclic aromatic hydrocarbons (PAHs) measured in the UV-Visible-NIR range in an astrophysically relevant environment. This type of measurements provides data on PAHs and nanometer-sized particles that can now be directly compared to astronomical spectra of the UV interstellar (IS) extinction curve and of the diffuse interstellar bands (DIBs). The harsh physical conditions of the IS medium - characterized by a low temperature, an absence of collisions and strong VUV radiation fields - are simulated in the laboratory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. This source combines a pulsed slit supersonic free jet expansion of argon seeded with PAHs (Salama, F., Allamandola, L. J. & Scherer, J. J., `Pulsed discharge nozzle cavity ringdown spectroscopy of cold PAH ions', J. Chem Phys.;in press) that have been pre-selected from Matrix Isolation Spectroscopy (MIS) studies. The absorption spectrum of the Pyrene cation (C16H10+) has also been measured. These experiments provide unique information on the spectra of free, large carbon-containing molecules and ions in the gas phase. The electronic bands measured for this selection of PAH ions are all found to be intrinsically broad (>˜20 cm-1). The laboratory data are compared with recent astronomical spectra of large DIBs. Preliminary results also show that carbon nanoparticles (˜2 nm size) are formed during the short residence time of the precursors in the plasma. This finding holds great potential for the spectroscopy of nanoparticles isolated in the gas-phase in an interstellar-like environment and for understanding the formation process of interstellar grains.

  2. Photoisomerization action spectroscopy of the carbocyanine dye DTC+ in the gas phase.

    Science.gov (United States)

    Adamson, Brian D; Coughlan, Neville J A; da Silva, Gabriel; Bieske, Evan J

    2013-12-19

    Molecular photoisomerization plays a crucial role in diverse biological and technological contexts. Here, we combine ion mobility spectrometry and laser spectroscopy to characterize the photoisomerization of molecular cations in the gas phase. The target molecular ions, polymethine dye cations 3,3'-diethylthiacarbocyanine (DTC(+)), are propelled through helium buffer gas by an electric field and are photoisomerized by light from a tunable laser. Photoexcitation over the 450-570 nm range converts trans-DTC(+) to cis-DTC(+), noticeably modifying the ions' arrival time distribution. The photoisomerization action spectrum, which has a maximum at 535 nm, resembles the absorption spectrum of DTC(+) in solution but is shifted 25 nm to shorter wavelength. Comparisons between measured and calculated mobilities suggest that the photoisomer involves a twist about the second C-C bond in the methine chain (8,9-cis isomer) rather than a twist about the first methine C-C bond (2,8-cis isomer). It is postulated that the excited gas-phase ions internally convert from the S1 Franck-Condon region to the S0 manifold and explore the conformational landscape as they cool through He buffer gas collisions. Master equation simulations of the relaxation process in the S0 manifold suggest that the 8,9-cis isomer is preferred over the 2,8-cis isomer because it lies lower in energy and because it is separated from the trans isomer by a substantially higher barrier. The study demonstrates that the photoisomerization of molecular ions can be probed selectively in the gas phase, providing insights into photoisomerization mechanisms and information on the solvent-free absorption spectrum.

  3. Are ionic liquids pairwise in gas phase? A cluster approach and in situ IR study.

    Science.gov (United States)

    Dong, Kun; Zhao, Lidong; Wang, Qian; Song, Yuting; Zhang, Suojiang

    2013-04-28

    In this work, we discussed the vaporization and gas species of ionic liquids (ILs) by a cluster approach of quantum statistical thermodynamics proposed by R. Luwig (Phys. Chem. Chem. Phys., 10, 4333), which is a controversial issue up to date. Based on the different sized clusters (2-12 ion-pairs) of the condensed phase, the molar enthalpies of vaporization (ΔvapH, 298.15 K, 1bar) of four representative ILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][NTf2]) 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([Emmim][NTf2]) 1-ethyl-3-methylimidazolium chloride ([Emim]Cl) and ethylammonium nitrate ([EtAm][NO3]), were calculated. The predicted ΔvapH were increased remarkably; even the values of [EtAm][NO3] were larger than 700 kJ mol(-1) when the charged isolated ions were assumed to be gas species. However, the ΔvapH were close to experimental measurements when the gas species assumed to be anion-cation pairwise, indicating that the different conformational ion-pairs can coexist in the gas phase when the IL is evaporated. Particularly for the protic IL, [EtAm][NO3], even the neutral precursor molecules by proton transfer can occur in gas phase. In addition, it's found that the effect of hydrogen bonds on the vaporization cannot be negligible by comparing the ΔvapH of [Emim][NTf2] with [Emmim][NTf2]. The in situ and calculated IR spectra provided the further proof that the ions are pairwise in gas phase.

  4. An approximate calculation of advective gas-phase transport of 14C at Yucca Mountain, Nevada

    Science.gov (United States)

    Knapp, R. B.

    1990-01-01

    A quasilinear partial differential equation, which describes gas-phase transport of a 14C kinematic wave through a porous medium, is derived, its sensitivity to system variables is analyzed and it is applied to one possible release scenarion at the porposed Yucca Mountain, Nevada high-level radioactive waste repository. Advection, isotope exchange between CO 2 in a flowing gas phase and HCO 3- in a static aqueous phase, and radioactive decay are incorporated. The governing equation is solved analytically by the method of characteristics. The mass fraction of 14C in the gas phase,X 14g, is controlled by radioactive decay. The relatively long half-line of 14C, about 5720 years, and the relatively shallow proposed burial depth of the radioactive waste, about 350m, requires significant retardation of the 14C wave velocity for significant reduction in X 14g. 14C wave velocity is most sensitive to temperature and pH which control the distribution of total carbon between gas and liquid phase; the greater the partitioning of carbon into the liquid phase, the greater the retardation of the 14C wave velocity and the greater the ultimate reduction in X 14g from initial conditions. Partitioning of total carbon into the liquid phase is greatest at low temperatures, 8. Increasing water saturation also tends to retard 14C wave velocity but to a lesser extent. The governing equation has been applied using conditions that may possibly occur at the proposed Yucca Mountain repository. Calculations indicate that the 14C wave takes about 5900 years to reach the surface with a X 14g equal to 25 ppm. Diffusion and dispersion are not of major importance for these conditions. These calculations are approximate due to the number of assumptions involved. Discharge of 14C into the gas before the selected time would accelerate wave arrival and increase the amount of 14C reaching the surface.

  5. Position for determining gas-phase volatile organic compound concentrations in transuranic waste containers. Revision 2

    Energy Technology Data Exchange (ETDEWEB)

    Connolly, M.J.; Liekhus, K.J. [Lockheed Martin Idaho Technologies Co., Idaho Falls, ID (United States). Idaho National Engineering and Environmental Lab.; Djordjevic, S.M.; Loehr, C.A.; Spangler, L.R. [Benchmark Environmental Corp. (United States)

    1998-06-01

    In the conditional no-migration determination (NMD) for the test phase of the Waste Isolation Pilot Plant (WIPP), the US Environmental Protection Agency (EPA) imposed certain conditions on the US Department of Energy (DOE) regarding gas phase volatile organic compound (VOC) concentrations in the void space of transuranic (TRU) waste containers. Specifically, the EPA required the DOE to ensure that each waste container has no layer of confinement that contains flammable mixtures of gases or mixtures of gases that could become flammable when mixed with air. The EPA also required that sampling of the headspace of waste containers outside inner layers of confinement be representative of the entire void space of the container. The EPA stated that all layers of confinement in a container would have to be sampled until DOE can demonstrate to the EPA that sampling of all layers is either unnecessary or can be safely reduced. A test program was conducted at the Idaho National Engineering and Environmental Laboratory (INEEL) to demonstrate that the gas phase VOC concentration in the void space of each layer of confinement in vented drums can be estimated from measured drum headspace using a theoretical transport model and that sampling of each layer of confinement is unnecessary. This report summarizes the studies performed in the INEEL test program and extends them for the purpose of developing a methodology for determining gas phase VOC concentrations in both vented and unvented TRU waste containers. The methodology specifies conditions under which waste drum headspace gases can be said to be representative of drum gases as a whole and describes a method for predicting drum concentrations in situations where the headspace concentration is not representative. The methodology addresses the approach for determining the drum VOC gas content for two purposes: operational period drum handling and operational period no-migration calculations.

  6. Enhanced Lipidome Coverage in Shotgun Analyses by using Gas-Phase Fractionation

    Science.gov (United States)

    Nazari, Milad; Muddiman, David C.

    2016-11-01

    A high resolving power shotgun lipidomics strategy using gas-phase fractionation and data-dependent acquisition (DDA) was applied toward comprehensive characterization of lipids in a hen ovarian tissue in an untargeted fashion. Using this approach, a total of 822 unique lipids across a diverse range of lipid categories and classes were identified based on their MS/MS fragmentation patterns. Classes of glycerophospholipids and glycerolipids, such as glycerophosphocholines (PC), glycerophosphoethanolamines (PE), and triglycerides (TG), are often the most abundant peaks observed in shotgun lipidomics analyses. These ions suppress the signal from low abundance ions and hinder the chances of characterizing low abundant lipids when DDA is used. These issues were circumvented by utilizing gas-phase fractionation, where DDA was performed on narrow m/z ranges instead of a broad m/z range. Employing gas-phase fractionation resulted in an increase in sensitivity by more than an order of magnitude in both positive- and negative-ion modes. Furthermore, the enhanced sensitivity increased the number of lipids identified by a factor of ≈4, and facilitated identification of low abundant lipids from classes such as cardiolipins that are often difficult to observe in untargeted shotgun analyses and require sample-specific preparation steps prior to analysis. This method serves as a resource for comprehensive profiling of lipids from many different categories and classes in an untargeted manner, as well as for targeted and quantitative analyses of individual lipids. Furthermore, this comprehensive analysis of the lipidome can serve as a species- and tissue-specific database for confident identification of other MS-based datasets, such as mass spectrometry imaging.

  7. Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2

    Science.gov (United States)

    Colombara, Diego; Berner, Ulrich; Ciccioli, Andrea; Malaquias, João C.; Bertram, Tobias; Crossay, Alexandre; Schöneich, Michael; Meadows, Helene J.; Regesch, David; Delsante, Simona; Gigli, Guido; Valle, Nathalie; Guillot, Jérome; El Adib, Brahime; Grysan, Patrick; Dale, Phillip J.

    2017-02-01

    Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.

  8. Information draft on the development of air standards for isopropyl benzene

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-01-01

    Isopropyl benzene, also commonly referred to as cumene, is a colourless liquid with a sharp, penetrating odour. It is derived from the distillation of coal tar, naphtha and petroleum. It is used mainly as an intermediate in the production of phenol, acetone, and alpha-methyl styrene, all of which are components in plastic resins. Isopropyl benzene is also used as a solvent and thinner for paints and enamels and as an octane booster in aviation gasoline. In 1996, reported atmospheric releases in Canada amounted to 16.4 tonnes, of which 9.1 tonnes were from Ontario sources. Isopropyl benzene is not a significant threat to health in low concentrations. Inhalation exposure can cause dizziness, light-headedness and fainting. Contact with isopropyl benzene can irritate the skin, eyes, nose and mouth. The current Ontario half-hour interim Point of Impingement (OPI) standard and the one-hour Ambient Air Quality Criterion (AAQC) are both set at 100 microgram/cubic meter on the basis of the odour nuisance property of the substance. A review of applicable literature from world-wide sources (and summarized in this report) reveal that four US agencies have developed air quality criteria for isopropyl benzene based on the health effects of the compound. These criteria range from 9 to 585 micrograms/cubic meter for an annual average basis and from 87 to 400 microgram/cubic meter on a 24-hour basis. 40 refs., 1 tab., appendix.

  9. BCS-BEC crossover and liquid-gas phase transition in nuclear matter

    Energy Technology Data Exchange (ETDEWEB)

    Jin Meng [Institute of Particle Physics and Physical Department, Central China Normal University, Wuhan 4300079 (China); Urban, Michael [Groupe de Physique Theorique, Institut de Physique Nucleaire -Centre Scientifique d' Orsay, F-91406 Orsay (France); Schuck, Peter, E-mail: jinm@iopp.ccnu.edu.cn [Laboratoire de Physique et Modelisation des Milieux Condenses,CNRS and Universite Joseph Fourier, BP 166, 38042 Grenoble Cedex (France)

    2011-09-16

    The effect of nucleon-nucleon correlations in symmetric nuclear matter at finite temperature is studied beyond BCS theory. We calculate the critical temperature for a BEC superfluid of deuterons, of a BCS superfluid of nucleons, and in the crossover between these limits. The effect of the correlations on the liquid-gas phase transition is discussed. Our results show that nucleon-nucleon correlations beyond BCS play an important role for the properties of nuclear matter, especially in the low-density region.

  10. Imaging molecular structure through femtosecond photoelectron diffraction on aligned and oriented gas-phase molecules

    OpenAIRE

    Boll, Rebecca; Rouzée, Arnaud; Christensen, Lauge; Coffee, Ryan; Coppola, Niccola; Sankar,; Decleva, Piero; Epp, Sascha W.; Erk, Benjamin; Filsinger, Frank; Foucar, Lutz; Gorkhover, Tais; Adolph, Marcus; Gumprecht, Lars; Hömke, André

    2014-01-01

    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump–probe setup combining optical lasers and an X-ray free-electron laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C8H5F) and dissociating, laser-aligned 1,4-dibromobenzene (C6H4Br2) molecules and discuss them in the larger context of photoelectron diffrac...

  11. Review: gas-phase ion chemistry of the noble gases: recent advances and future perspectives.

    Science.gov (United States)

    Grandinetti, Felice

    2011-01-01

    This review article surveys recent experimental and theoretical advances in the gas-phase ion chemistry of the noble gases. Covered issues include the interaction of the noble gases with metal and non-metal cations, the conceivable existence of covalent noble-gas anions, the occurrence of ion-molecule reactions involving singly-charged xenon cations, and the occurrence of bond-forming reactions involving doubly-charged cations. Research themes are also highlighted, that are expected to attract further interest in the future.

  12. Critical temperature for the nuclear liquid-gas phase transition (from multifragmentation and fission)

    CERN Document Server

    Karnaukhov, V A; Budzanowski, A; Avdeyev, S P; Botvina, A S; Cherepanov, E A; Karcz, W; Kirakosyan, V V; Rukoyatkin, P A; Skwirczynska, I; Norbeck, E

    2008-01-01

    Critical temperature Tc for the nuclear liquid-gas phase transition is stimated both from the multifragmentation and fission data. In the first case,the critical temperature is obtained by analysis of the IMF yields in p(8.1 GeV)+Au collisions within the statistical model of multifragmentation (SMM). In the second case, the experimental fission probability for excited 188Os is compared with the calculated one with Tc as a free parameter. It is concluded for both cases that the critical temperature is higher than 16 MeV.

  13. Wettability in the liquid Cu-Ag alloy – fireproof material – gas phase system

    Directory of Open Access Journals (Sweden)

    G. Siwiec

    2013-07-01

    Full Text Available In the present paper, results of wettability studies on the liquid metal – fireproof material – gas phase system using copper and Cu-Ag alloys as well as typical fireproof materials, i.e. aluminium oxide, magnesium oxide and graphite, are presented. Contact angle measurements were conducted at 1 373–1 573 K by means of a high-temperature microscope coupled with a camera and a computer equipped with a program for recording and analysing images. For the measurements, the sessile drop method was used.

  14. Going clean: structure and dynamics of peptides in the gas phase and paths to solvation

    Science.gov (United States)

    Baldauf, Carsten; Rossi, Mariana

    2015-12-01

    The gas phase is an artificial environment for biomolecules that has gained much attention both experimentally and theoretically due to its unique characteristic of providing a clean room environment for the comparison between theory and experiment. In this review we give an overview mainly on first-principles simulations of isolated peptides and the initial steps of their interactions with ions and solvent molecules: a bottom up approach to the complexity of biological environments. We focus on the accuracy of different methods to explore the conformational space, the connections between theory and experiment regarding collision cross section evaluations and (anharmonic) vibrational spectra, and the challenges faced in this field.

  15. Gas-phase oxidation of propane in the presence of azaporphin compounds

    Energy Technology Data Exchange (ETDEWEB)

    Enikobpov, N.S.; Moshkina, R.I.; Nikisha, L.V.; Polyak, S.S.; Promyslova, V.V.

    1985-07-01

    The gas-phase oxidation of an equimolar mixture of propane with oxygen was studied in the presence of various polyphthalocyanins: metal-free PPC and mono- and bimetallic complexes PPC-Fe, PPC-Co, PPC-Cu-Fe, and PPC-Mg-Fe. The inhibition of oxidation increases in the series: PPC-Co < PPC-Fe approx. = PPC-Mg-Fe < PPC < PPC-Cu-Fe. The qualitative and quantitative composition of the products is virtually unchanged in comparison with the untreated reactor.

  16. Simulation of Particle Growth in Gas Phase Polymerization of Butadiene by the Multigrain Model

    Institute of Scientific and Technical Information of China (English)

    孙建中; 赵军子; 何斯征; 周其云

    2001-01-01

    Gas phase polymerization of butadiene by neodymium catalyst was modeled. The effects of mass and heat transfer resistances in the external boundary layer and within particles, sorption of butadiene in polybutadiene,and deactivation of active sites on polymer particle growth and morphology were studied. Simulation results show that the effects of intraparticle mass and heat transfer resistances on the growth rate of polymer particles are insignificant, and that there is no significant effect of mass transfer resistance on the morphology of polymer particles.The simulation results were compared with the experimental results.

  17. Predicting dermal absorption of gas-phase chemicals: transient model development, evaluation, and application

    DEFF Research Database (Denmark)

    Gong, M.; Zhang, Y.; Weschler, Charles J.

    2014-01-01

    A transient model is developed to predict dermal absorption of gas-phase chemicals via direct air-to-skin-to-blood transport under non-steady-state conditions. It differs from published models in that it considers convective mass-transfer resistance in the boundary layer of air adjacent to the skin....... Results calculated with this transient model are in good agreement with the limited experimental results that are available for comparison. The sensitivity of the modeled estimates to key parameters is examined. The model is then used to estimate air-to-skin-to-blood absorption of six phthalate esters...

  18. The Significance of Gas-Phase Mass Transport in Assessment of kchem and Dchem

    DEFF Research Database (Denmark)

    Lohne, Ørjan Fossmark; Søgaard, Martin; Wiik, Kjell

    2013-01-01

    In this work, the validity of electrical conductivity relaxation (ECR) as a method for the assessment of chemical surface exchange, kchem, and bulk diffusion, Dchem, coefficients is investigated with respect to mass transport limitations in the gas phase. A model encompassing both the oxygen...... is evident and modeled apparent activation energies for kchem are shown to decrease significantly. A criteria for the validity of Dchem is introduced while no such measure could be introduced for kchem. The effect of experimental parameters and material properties on mass transport limitations are presented...

  19. Ab initio studies of aspartic acid conformers in gas phase and in solution

    Science.gov (United States)

    Chen, Mingliang; Lin, Zijing

    2007-10-01

    Systematic and extensive conformational searches of aspartic acid in gas phase and in solution have been performed. For the gaseous aspartic acid, a total of 1296 trial canonical structures and 216 trial zwitterionic structures were generated by allowing for all combinations of internal single-bond rotamers. All the trial structures were optimized at the B3LYP /6-311G* level and then subjected to further optimization at the B3LYP /6-311++G** level. A total of 139 canonical conformers were found, but no stable zwitterionic structure was found. The rotational constants, dipole moments, zero-point vibrational energies, harmonic frequencies, and vertical ionization energies of the canonical conformers were determined. Single-point energies were also calculated at the MP2/6-311++G** and CCSD /6-311++G** levels. The equilibrium distributions of the gaseous conformers at various temperatures were calculated. The proton affinity and gas phase basicity were calculated and the results are in excellent agreement with the experiments. The conformations in the solution were studied with different solvation models. The 216 trial zwitterionic structures were first optimized at the B3LYP /6-311G* level using the Onsager self-consistent reaction field model (SCRF) and then optimized at the B3LYP /6-311++G** level using the conductorlike polarized continuum model (CPCM) SCRF theory. A total of 22 zwitterions conformers were found. The gaseous canonical conformers were combined with the CPCM model and optimized at the B3LYP /6-311++G** level. The solvated zwitterionic and canonical structures were further examined by the discrete/SCRF model with one and two water molecules. The incremental solvation of the canonical and zwitterionic structures with up to six water molecules in gas phase was systematically examined. The studies show that combining aspartic acid with at least six water molecules in the gas phase or two water molecules and a SCRF solution model is required to provide

  20. Effect of chloralkanes on the phenyltrichlorosilane synthesis by gas phase condensation

    Institute of Scientific and Technical Information of China (English)

    Tong Liu; Yunlong Huang; Chao Wang; Qiang Tang; Jinfu Wang

    2015-01-01

    To enhance the process of phenyltrichlorosilane synthesis using gas phase condensation, a series of chloralkanes were introduced. The influence of temperature and chloralkane amount on the synthesis was studied based on the product distribution from a tubular reactor. The promoting effect of chloralkane addition was mainly caused by the chloralkane radicals generated by the dissociation of C–Cl bond. The promoting effect of the chloromethane with more chlorine atoms was better than those with less chlorine atoms. Intermediates detected from the reactions with isoprene and bromobenzene demonstrated that both trichlorosilyl radical and dichlorosilylene existed in the reaction system in the presence of chloralkanes. A detailed reaction scheme was proposed.

  1. Gas Phase Chromatography of some Group 4, 5, and 6 Halides

    Energy Technology Data Exchange (ETDEWEB)

    Sylwester, Eric Robert [Univ. of California, Berkeley, CA (United States)

    1998-10-01

    Gas phase chromatography using The Heavy Element Volatility Instrument (HEVI) and the On Line Gas Apparatus (OLGA III) was used to determine volatilities of ZrBr4, HfBr4, RfBr4, NbBr5, TaOBr3, HaCl5, WBr6, FrBr, and BiBr3. Short-lived isotopes of Zr, Hf, Rf, Nb, Ta, Ha, W, and Bi were produced via compound nucleus reactions at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory and transported to the experimental apparatus using a He gas transport system. The isotopes were halogenated, separated from the other reaction products, and their volatilities determined by isothermal gas phase chromatography. Adsorption Enthalpy (ΔHa) values for these compounds were calculated using a Monte Carlo simulation program modeling the gas phase chromatography column. All bromides showed lower volatility than molecules of similar molecular structures formed as chlorides, but followed similar trends by central element. Tantalum was observed to form the oxybromide, analogous to the formation of the oxychloride under the same conditions. For the group 4 elements, the following order in volatility and ΔHa was observed: RfBr4 > ZrBr4 > HfBr4. The ΔHa values determined for the group 4, 5, and 6 halides are in general agreement with other experimental data and theoretical predictions. Preliminary experiments were performed on Me-bromides. A new measurement of the half-life of 261Rf was performed. 261Rf was produced via the 248Cm(18O, 5n) reaction and observed with a half-life of 74-6+7 seconds, in excellent agreement with the previous measurement of 78-6+11 seconds. We recommend a new half-life of 75±7 seconds for 261Rf based on these two measurements. Preliminary studies in transforming HEVI from an isothermal (constant

  2. Ab initio treatment of gas phase GeO2+ doubly charged ion

    Science.gov (United States)

    Mogren Al Mogren, M.; Ben Abdallah, D.; Hochlaf, M.

    2015-01-01

    Using multi reference configuration interaction methodology in connection with a large basis set, we show that GeO2+ is a metastable species either in the ground or in the electronically excited states. This confirms the observation of this dication in gas phase by mass spectrometry. In addition, we derived a set of accurate spectroscopic terms for GeO2+ bound states. At the MRCI/aug-cc-pV5Z level of theory, the adiabatic double ionization energy of GeO is computed to be ∼28.93 eV.

  3. Enantioselective supramolecular devices in the gas phase. Resorcin[4]arene as a model system

    Directory of Open Access Journals (Sweden)

    Caterina Fraschetti

    2012-04-01

    Full Text Available This review describes the state-of-art in the field of the gas-phase reactivity of diastereomeric complexes formed between a chiral artificial receptor and a biologically active molecule. The presented experimental approach is a ligand-displacement reaction carried out in a nano ESI-FT-ICR instrument, supported by a thermodynamic MS-study and molecular-mechanics and molecular-dynamics (MM/MD computational techniques. The noncovalent ion–molecule complexes are ideal for the study of chiral recognition in the absence of complicating solvent and counterion effects.

  4. Gas phase NMR spectra of N,N-dimethylnitrosamine. Environmental effects on kinetic parameters

    Science.gov (United States)

    Chauvel, J. Paul; Leung, Doris Y.; True, Nancy S.

    1984-04-01

    Gas phase 1H NMR spectra of N,N-dimethylnitrosamine are consistent with first order chemical exchange rate constants which are ca. 25 times faster than those observed in neat liquids at corresponding temperatures. The associated kinetic parameters: Eact(∞), 20.5(1.1) kcal mol -1, Δ H‡, 19.7(1.0) kcal mol -1 and Δ G‡, 21.1(0.4) kcal mol -1 are approximately 2.5 kcal mol -1 lower than the most recently reported values for the neat liquid. The observed phase dependence is consistent with a process proceeding via a freely rotating transition state.

  5. The two-dimensional alternative binary L-J system: liquid-gas phase diagram

    Institute of Scientific and Technical Information of China (English)

    张陟; 陈立溁

    2003-01-01

    A two-dimensional (2D) binary system without considering the Lennard-Jones (L-J) potential has been studied by using the Collins model. In this paper, we introduce the L-J potential into the 2D binary system and consider the existence of the holes that are called the "molecular fraction". The liquid-gas phase diagram of the 2D alternative binary L-J system is obtained. The results are quite analogous to the behaviour of 3D substances.

  6. Gas phase detection of the NH-P hydrogen bond and importance of secondary interactions

    DEFF Research Database (Denmark)

    Møller, Kristian Holten; Hansen, Anne Schou; Kjærgaard, Henrik Grum

    2015-01-01

    We have observed the NH···P hydrogen bond in a gas phase complex. The bond is identified in the dimethylamine-trimethylphosphine complex by a red shift of the fundamental NH-stretching frequency observed using Fourier transform infrared spectroscopy (FT-IR). On the basis of the measured NH-stretc......3LYP-D3BJ, CAM-B3LYP, and ωB97X-D, as well as MP2, show comparable contributions from the hydrogen bond and the secondary interactions and are close to DF-LCCSD(T)-F12a results....

  7. Studies on Macro—kinetics of Gas Phase Polymerization of Butadiene with Rare—earch Catalyst

    Institute of Scientific and Technical Information of China (English)

    FANGDonyu; SUNJianzhong; 等

    2002-01-01

    The study of the kinetics of gas phase polymerization of butadiene with heterogeneous catalyst based on neodymium(Nd) was carried out.The effects of reaction temperature,reaction pressure,dispersing medium, and types of catalyst on kinetics of polymerization were investigated .A kinetic model with two kinds of active sites was proposed.The results show that the effects of the reaction temperature and the types of dispersing medium and catalyst on the kinetic performance of polymerization are significant,and that the combined model of first and second order decay of active site of catalyst can be used to describe the phenomena.

  8. Gas-phase production of single-walled carbon nanotubes from carbon monoxide: a review of the hipco process

    Science.gov (United States)

    Nikolaev, Pavel

    2004-01-01

    The latest process for producing large quantities of single-walled carbon nanotubes (SWNTs) to emerge from the Rice University, dubbed HiPco, is living up to its promise. The current production rates approach 450 mg/h (or 10 g/day), and nanotubes typically have no more than 7 mol % of iron impurities. Second-generation HiPco apparatus can run continuously for 7-10 days at a time. In the HiPco process nanotubes grow in high-pressure, high-temperature flowing CO on catalytic clusters of iron. Catalyst is formed in situ by thermal decomposition of iron pentacarbonyl, which is delivered intact within a cold CO flow and then rapidly mixed with hot CO in the reaction zone. Upon heating, the Fe(CO)5 decomposes into atoms that condense into larger clusters. SWNTs nucleate and grow on these particles in the gas phase via CO disproportionation: CO + CO --> CO2 + C (SWNT), catalyzed by the Fe surface. The concentration of CO2 produced in this reaction is equal to that of carbon and can therefore serve as a useful real-time feedback parameter. It was used to study and optimize SWNT production as a function of temperature, pressure, and Fe(CO)5 concentration. The results of the parametric study are in agreement with current understanding of the nanotube formation mechanism.

  9. Effects of inert species in the gas phase in a model for the catalytic oxidation of CO

    CERN Document Server

    Buendia, G M

    2011-01-01

    We study by kinetic Monte Carlo simulations the catalytic oxidation of carbon monoxide on a surface in the presence of contaminants in the gas phase. The process is simulated by a Ziff-Gulari-Barshad (ZGB) model that has been modified to include the effect of the contaminants and to eliminate the unphysical oxygen-poisoned phase. The impurities can adsorb and desorb on the surface, but otherwise remain inert. We find that, if the impurities can not desorb, no matter how small their proportion in the gas mixture, the first order transition and the reactive window that characterize the ZGB model disappear. The coverages become continuous, and once the surface has reached a steady state there is no production of CO$_2$. This is quite different from the behavior of a system in which the surface presents a fixed percentage of impurities. When the contaminants are allowed to desorb, the reactive window appears again, and disappears at a value that depends on the proportion of contaminants in the gas and on their de...

  10. Silanization of silica and glass slides for DNA microarrays by impregnation and gas phase protocols: A comparative study

    Energy Technology Data Exchange (ETDEWEB)

    Phaner-Goutorbe, Magali, E-mail: Magali.Phaner@ec-lyon.fr [Universite de Lyon, Institut des Nanotechnologies de Lyon UMR 5270, Ecole Centrale de Lyon, 36 avenue Guy de Collongue, 69134 Ecully (France); Dugas, Vincent, E-mail: Vincent.Dugas@univ-lyon1.fr [Universite de Lyon, Universite Claude Bernard Lyon 1, Laboratoire des sciences analytiques UMR 5180, 43, bd du 11 Novembre 1918, 69622 Villeurbanne cedex (France); Chevolot, Yann, E-mail: Yann.Chevolot@ec-lyon.fr [Universite de Lyon, Institut des Nanotechnologies de Lyon UMR 5270, Ecole Centrale de Lyon, 36 avenue Guy de Collongue, 69134 Ecully (France); Souteyrand, Eliane, E-mail: Eliane.Souteyrand@ec-lyon.fr [Universite de Lyon, Institut des Nanotechnologies de Lyon UMR 5270, Ecole Centrale de Lyon, 36 avenue Guy de Collongue, 69134 Ecully (France)

    2011-03-12

    Surface immobilization of oligonucleotide probes (oligoprobes) is a key issue in the development of DNA-chips. The immobilization protocol should guarantee good availability of the probes, low non-specific adsorption and reproducibility. We have previously reported a silanization protocol with tert-butyl-11-(dimethylamino)silylundecanoate performed by impregnation (Impregnation Protocol, IP) of silica substrates from dilute silane solutions, leading to surfaces bearing carboxylic groups. In this paper, the Impregnation protocol is compared with a Gas phase Protocol (GP) which is more suited to industrial requirements such as reliable and robust processing, cost efficiency, etc.... The morphology of the oligoprobe films at the nanoscale (characterized by Atomic Force Microscopy) and the reproducibility of subsequent oligoprobes immobilization steps have been investigated for the two protocols on thermal silica (Si/SiO{sub 2}) and glass slide substrates. IP leads to smooth surfaces whereas GP induces the formation of islands features suggesting a non-continuous silane layer. The reproducibility of the overall surface layer (18.75 mm{sup 2}) has been evaluated through the covalent immobilization of a fluorescent oligoprobes. Average fluorescent signals of 6 (a.u.) and 4 (a.u.) were observed for IP and GP, respectively, with a standard deviation of 1 for both protocols. Thus, despite a morphological difference of the silane layer at the nanometer scale, the density of the immobilized probes remained similar.

  11. Photocatalytic oxidation of H2S in the gas phase over TiO2-coated glass fiber filter.

    Science.gov (United States)

    Brancher, Marlon; Franco, Davide; de Melo Lisboa, Henrique

    2016-11-01

    To promote the photocatalytic oxidation (PCO) of hydrogen sulfide (H2S) in the gas phase, TiO2-coated glass fiber filters were packed in an annular photoreactor. Glass fibers coated with TiO2 thin films were characterized structurally and morphologically by field emission gun scanning electron microscopy (FEG-SEM), scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS) and X-ray diffractometry (XRD). Flow rate and H2S inlet concentration were evaluated to determine the performance of the reactor. Removal efficiencies up to 99% were achieved for flow rate of 25 L h(-1) (residence time of 121 s) and H2S inlet concentration from 12 to 14 ppmv. The long-term experiment presented H2S removal of 89% for 16 h. After 28 h of continuous use, H2S degradation was observed at 64%, which suggests that the photocatalyst was losing activity due to deactivation. Moreover, the kinetics of the PCO of H2S according to the Langmuir-Hinshelwood (L-H) approach along with the mass balance of a plug-flow reactor was modeled. The reaction constant (k) was calculated at approximately 10.5 μmol m(-3) s(-1) and the adsorption constant (K) of approximately 5263 m(-3) mol with linearity (R2) of 0.98.

  12. Hydroperoxide Measurements During Low-Temperature Gas-Phase Oxidation of n-Heptane and n-Decane

    KAUST Repository

    Rodriguez, Anne

    2017-02-13

    A wide range of hydroperoxides (C-C alkyl hydroperoxides, C-C alkenyl hydroperoxides, C ketohydroperoxides, and hydrogen peroxide (HO)), as well as ketene and diones, have been quantified during the gas-phase oxidation of n-heptane. Some of these species, as well as C alkenyl hydroperoxides and ketohydroperoxides, were also measured during the oxidation of n-decane. These experiments were performed using an atmospheric-pressure jet-stirred reactor at temperatures from 500 to 1100 K and one of three analytical methods, time-of-flight mass spectrometry combined with tunable synchrotron photoionization with a molecular beam sampling: time-of-flight mass spectrometry combined with laser photoionization with a capillary tube sampling, continuous wave cavity ring-down spectroscopy with sonic probe sampling. The experimental temperature at which the maximum mole fraction is observed increases significantly for alkyl hydroperoxides, alkenyl hydroperoxides, and then more so again for hydrogen peroxide, compared to ketohydroperoxides. The influence of the equivalence ratio from 0.25 to 4 on the formation of these peroxides has been studied during n-heptane oxidation. The up-to-date detailed kinetic oxidation models for n-heptane and for n-decane found in the literature have been used to discuss the possible pathways by which these peroxides, ketene, and diones are formed. In general, the model predicts well the reactivity of the two fuels, as well as the formation of major intermediates. (Figure Presented).

  13. OPTIMIZATION OF DEHYDRATION CONDITIONS FOR ISOPROPYL ALCOHOL – WATER MIXTURE USING OXIDIZED POTATO STARCH

    Directory of Open Access Journals (Sweden)

    P.C.N EJIKEME

    2012-12-01

    Full Text Available This study investigated the possibility of dehydrating Isopropyl Alcohol – water mixture using oxidized starch from potato. The starch was modified using calcium hypochlorite. Central composite design was used to determine the effects of the four dehydrating variables; temperature, contact time, initial concentration of the isopropyl alcohol water solution and the adsorbent/solution ratio on the final concentration of the isopropyl alcohol water mixture. Based on the central composite design, a quadratic verses 2 factor interaction model was developed. The significant factors on the experimental design response were identified from the analysis of variance. The optimum conditions for the dehydration reaction were obtained by using temperature of 35oC, time of 40 minutes, adsorbent/solution ratio of 1:4 and initial concentration of 40% which resulted in finalconcentration of 43.968%.

  14. GLASS: gas-phase metallicity and radial gradients in an interacting system at z~2

    CERN Document Server

    Jones, Tucker; Schmidt, Kasper; Treu, Tommaso; Brammer, Gabriel; Bradac, Marusa; Dressler, Alan; Henry, Alaina; Malkan, Matthew; Pentericci, Laura; Trenti, Michele

    2014-01-01

    We present spatially resolved gas-phase metallicity for a system of three galaxies at z=1.85 detected in the Grism Lensed-Amplified Survey from Space (GLASS). The combination of HST's diffraction limit and strong gravitational lensing by the cluster MACS J0717+3745 results in a spatial resolution of ~200-300 pc, enabling good spatial sampling despite the intrinsically small galaxy sizes. The galaxies in this system are separated by 50-200 kpc in projection and are likely in an early stage of interaction, evidenced by relatively high specific star formation rates. Their gas-phase metallicities are consistent with larger samples at similar redshift, star formation rate, and stellar mass. We obtain a precise measurement of the metallicity gradient for one galaxy and find a shallow slope compared to isolated galaxies at high redshift, consistent with a flattening of the gradient due to gravitational interaction. An alternative explanation for the shallow metallicity gradient and elevated star formation rate is ra...

  15. Biofiltration of mixtures of gas-phase styrene and acetone with the fungus Sporothrix variecibatus

    Energy Technology Data Exchange (ETDEWEB)

    Rene, Eldon R.; Spackova, Radka; Veiga, Maria C. [University of La Coruna, Dpt. of Chemical Engineering, Campus da Zapateira, Rua da Fraga, 10, 15008 La Coruna (Spain); Kennes, Christian, E-mail: kennes@udc.es [University of La Coruna, Dpt. of Chemical Engineering, Campus da Zapateira, Rua da Fraga, 10, 15008 La Coruna (Spain)

    2010-12-15

    The biodegradation performance of a biofilter, inoculated with the fungus Sporothrix variecibatus, to treat gas-phase styrene and acetone mixtures under steady-state and transient conditions was evaluated. Experiments were carried out by varying the gas-flow rates (0.05-0.4 m{sup 3} h{sup -1}), leading to empty bed residence times as low as 17.1 s, and by changing the concentrations of gas-phase styrene (0.01-6.3 g m{sup -3}) and acetone (0.01-8.9 g m{sup -3}). The total elimination capacities were as high as 360 g m{sup -3} h{sup -1}, with nearly 97.5% removal of styrene and 75.6% for acetone. The biodegradation of acetone was inhibited by the presence of styrene, while styrene removal was affected only slightly by the presence of acetone. During transient-state experiments, increasing the overall pollutant load by almost 3-fold, i.e., from 220 to 600 g m{sup -3} h{sup -1}, resulted in a sudden drop of removal efficiency (>90-70%), but still high elimination capacities were maintained. Periodic microscopic observations revealed that the originally inoculated Sporothrix sp. remained present in the reactor and actively dominant in the biofilm.

  16. LIF-imaging and gas-phase diagnostics of laser desorbed MALDI-matrix plumes

    Energy Technology Data Exchange (ETDEWEB)

    Puretzky, A.A.; Geohegan, D.B. [Oak Ridge National Lab., TN (United States). Solid State Div.

    1997-07-01

    The first gated LIF-imaging and absorption spectroscopy has been performed on laser desorbed plumes from organic crystals which are commonly used as MALDI (Matrix Assisted Laser Desorption Ionization) matrices. These plasma diagnostic techniques, including ion probe measurements were employed to investigate the desorbed products, densities, fractional ionization, and velocity distributions of the plume of ejecta which is typically employed as the main desorption product in the mass spectrometry analysis of large biomolecules. Ultraviolet pulsed 193-nm and 248-nm irradiation of 3-hydroxypicolinic acid (3-HPA) crystals were studied to understand the effect of very different gas-phase absorption cross sections measured here for this material. In both cases, LIF imaging revealed two plume components: a fast (maximum {approximately} 0.1 cm/{micro}s) low-intensity component which appear to be 3-HPA fragments, and a slower component of 3-HPA expanding at 0.05 cm/{micro}s. In the case of ArF-laser irradiation, optical absorption spectroscopy indicated a breaking of the intramolecular hydrogen bond in the gas-phase matrix material.

  17. Direct Time-domain Observation of Conformational Relaxation in Gas-phase Cold Collisions

    CERN Document Server

    Drayna, Garrett K; Wang, Kenneth; Domingos, Sergio R; Eibengerber, Sandra; Doyle, John M; Patterson, David

    2016-01-01

    Cooling molecules in the gas phase is important for precision spectroscopy, cold molecule physics, and physical chemistry. Measurements of conformational relaxation cross sections shed important light on potential energy surfaces and energy flow within a molecule. However, gas-phase conformational cooling has not been previously observed directly. In this work, we directly observe conformational dynamics of 1,2-propanediol in cold (6K) collisions with atomic helium using microwave spectroscopy and buffer-gas cooling. Precise knowledge and control of the collisional environment in the buffer-gas allows us to measure the absolute collision cross-section for conformational relaxation. Several conformers of 1,2-propanediol are investigated and found to have relaxation cross-sections with He ranging from $\\sigma=4.7(3.0)\\times10^{-18}\\:\\mathrm{cm}^{2}$ to $\\sigma>5\\times10^{-16}\\:\\mathrm{cm}^{2}$. Our method is applicable to a broad class of molecules and could be used to provide information about the potential en...

  18. Chemical deposition from gas phase of the hetero and nanostructures of III–V compounds

    Directory of Open Access Journals (Sweden)

    Voronin V. A.

    2008-10-01

    Full Text Available This is a report of experimental result in-situ metod UV-Spectroscopy on the gas phase composition in the source region GaAs, GaP, In, Ga, In/Ga of gas-flov reactor. The kinetics of individual reactions was determined for a wide range of flow rates and temperatures. The received experimental data were used to analyze the epilayers deposition of GaAs:Bi, GaAs1–хPх, In1–хGaхAs, InхGa1–хAsуP1–у, by the low temperature Isothermal Vapor Phase Epitaxy (I-VPE method. The analysis of processes taking place in a zone of a source is necessary to understand the influence of such technological parameters as temperature, gas flow rate of the carrier, entering concentrations of components on composition and formation rate of supersaturated gas phase the low temperature growth getero nanostruction GaAs, GaAs1–хPх, In1–хGaхAs, InхGa1–хAsуP1–у.

  19. Nanoparticles-chemistry, new synthetic approaches, gas phase clustering and novel applications

    Indian Academy of Sciences (India)

    A Sreekumaran Nair; Chandramouli Subramaniam; M J Rosemary; Renjis T Tom; V R Rajeev Kumar; D M David Jeba Singh; Jobin Cyriac; Prashant Jain; K A Kalesh; Shreya Bhattacharya; T Pradeep

    2005-10-01

    In this paper, an overview of the synthesis, chemistry and applications of nanosystems carried out in our laboratory is presented. The discussion is divided into four sections, namely (a) chemistry of nanoparticles, (b) development of new synthetic approaches, (c) gas phase clusters and (d) device structures and applications. In `chemistry of nanoparticles' we describe a novel reaction between nanoparticles of Ag and Au with halocarbons. The reactions lead to the formation of various carbonaceous materials and metal halides. In `development of new synthetic approaches' our one-pot methodologies for the synthesis of core-shell nanosystems of Au, Ag and Cu protected with TiO2 and ZrO2 as well as various polymers are discussed. Some results on the interaction of nanoparticles with biomolecules are also detailed in this section. The third section covers the formation of gas phase aggregates/clusters of thiol-protected sub-nanoparticles. Laser desorption of H2MoO4, H2WO4, MoS2, and WS2 giving novel clusters is discussed. The fourth section deals with the development of simple devices and technologies using nanomaterials described above.

  20. Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

    Science.gov (United States)

    Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

    2016-09-01

    The gas-phase oxidation of doubly protonated peptides containing neutral basic residues to various products, including [M + H + O]+, [M - H]+, and [M - H - NH3]+, is demonstrated here via ion/ion reactions with periodate. It was previously demonstrated that periodate anions are capable of oxidizing disulfide bonds and methionine, tryptophan, and S-alkyl cysteine residues. However, in the absence of these easily oxidized sites, we show here that systems containing neutral basic residues can undergo oxidation. Furthermore, we show that these neutral basic residues primarily undergo different types of oxidation (e.g., hydrogen abstraction) reactions than those observed previously (i.e., oxygen transfer to yield the [M + H + O]+ species) upon gas-phase ion/ion reactions with periodate anions. This chemistry is illustrated with a variety of systems, including a series of model peptides, a cell-penetrating peptide containing a large number of unprotonated basic sites, and ubiquitin, a roughly 8.6 kDa protein.

  1. A comparative study of interatomic potentials for copper and aluminum gas phase sputter atom transport simulations

    CERN Document Server

    Kuwata, K T; Doyle, J R

    2003-01-01

    A comparative study of interatomic potential models for use in gas phase sputter atom transport simulations is presented. Quantum chemical interatomic potentials for argon-copper and argon-aluminum are calculated using Kohn-Sham density functional theory utilizing the PW91 functional. These potentials (PW91) are compared to the commonly used Born-Mayer potentials calculated by Abrahamson [Phys. Rev. 178 (1969) 76] using the Thomas-Fermi-Dirac model (TFD) and the screened Coulomb potentials derived from the 'universal' form calculated by Ziegler, Biersack and Littmark (ZBL). Monte Carlo simulations of gas phase sputter atom transport were performed to determine the average energy of atoms arriving at the substrate versus pressure for the three potential models. Overall, the ZBL potential gave results in much better agreement with the PW91 potential than the TFD potential. A characteristic thermalization pressure-distance product of approx 0.11 mTorr cm was found for both copper and aluminum using the PW91 pote...

  2. The experimental and theoretical gas phase acidities of adenine, guanine, cytosine, uracil, thymine and halouracils

    Science.gov (United States)

    Chen, Edward C. M.; Herder, Charles; Chen, Edward S.

    2006-10-01

    The gas phase acidities GPA (Δ H (298) for deprotonation) of the most stable tautomers of adenine, guanine, cytosine, uracil and thymine are evaluated. New GPA are obtained from electron impact spectra and acid dissociation constants measured in dimethylsulfoxide for A, U and 5-FU. The average experimental GPA are: [N1 sbnd H] C 340(2); T 333(2); U 333(2); 5-FU 329(4); [N9 sbnd H] A 333(1); G 332(4); all in kcal/mol. Only cytosine is a weaker acid than HCl in the gas phase. The most acidic hydrogens in the nucleotides are replaced by the sugar in DNA and RNA. The experimental N3 sbnd H GPA are G 334(4); U 347(2), T 347(4), while the predicted N3 sbnd H 5-FU GPA is 343 kcal/mol. The NH sbnd H GPA are: C 346(4); A 352(2); G 336(4) (all in kcal/mol). These are supported by semi-empirical multiconfiguration configuration interaction calculations. The predicted C8 sbnd H acidities of G and A and the C6 sbnd H of T are about the same, 360(2) kcal/mol. The remaining CH acidities are 370-380 kcal/mol. The 5-halouracils are predicted to be more acidic than HCl.

  3. First detection of gas-phase ammonia in a planet-forming disk

    CERN Document Server

    Salinas, Vachail N; Bergin, Edwin A; Cleeves, L Ilsedore; Brinch, Christian; Blake, Geoffrey A; Lis, Dariusz C; Melnick, Gary J; Panić, Olja; Pearson, John C; Kristensen, Lars; Yıldız, Umut A; van Dishoeck, Ewine F

    2016-01-01

    Nitrogen chemistry in protoplanetary disks and the freeze-out on dust particles is key to understand the formation of nitrogen bearing species in early solar system analogs. So far, ammonia has not been detected beyond the snowline in protoplanetary disks. We aim to find gas-phase ammonia in a protoplanetary disk and characterize its abundance with respect to water vapor. Using HIFI on the Herschel Space Observatory we detect, for the first time, the ground-state rotational emission of ortho-NH$_3$ in a protoplanetary disk, around TW Hya. We use detailed models of the disk's physical structure and the chemistry of ammonia and water to infer the amounts of gas-phase molecules of these species. We explore two radial distributions ( confined to $<$60 au like the millimeter-sized grains) and two vertical distributions (near the midplane where water is expected to photodesorb off icy grains) to describe the (unknown) location of the molecules. These distributions capture the effects of radial drift and vertical...

  4. Enhanced Basicity of Push-Pull Nitrogen Bases in the Gas Phase.

    Science.gov (United States)

    Raczyńska, Ewa D; Gal, Jean-François; Maria, Pierre-Charles

    2016-11-23

    Nitrogen bases containing one or more pushing amino-group(s) directly linked to a pulling cyano, imino, or phosphoimino group, as well as those in which the pushing and pulling moieties are separated by a conjugated spacer (C═X)n, where X is CH or N, display an exceptionally strong basicity. The n-π conjugation between the pushing and pulling groups in such systems lowers the basicity of the pushing amino-group(s) and increases the basicity of the pulling cyano, imino, or phosphoimino group. In the gas phase, most of the so-called push-pull nitrogen bases exhibit a very high basicity. This paper presents an analysis of the exceptional gas-phase basicity, mostly in terms of experimental data, in relation with structure and conjugation of various subfamilies of push-pull nitrogen bases: nitriles, azoles, azines, amidines, guanidines, vinamidines, biguanides, and phosphazenes. The strong basicity of biomolecules containing a push-pull nitrogen substructure, such as bioamines, amino acids, and peptides containing push-pull side chains, nucleobases, and their nucleosides and nucleotides, is also analyzed. Progress and perspectives of experimental determinations of GBs and PAs of highly basic compounds, termed as "superbases", are presented and benchmarked on the basis of theoretical calculations on existing or hypothetical molecules.

  5. Comparison of electrical and optical characteristics in gas-phase and gas-liquid phase discharges

    Science.gov (United States)

    Qazi, H. I. A.; Nie, Qiu-Yue; Li, He-Ping; Zhang, Xiao-Fei; Bao, Cheng-Yu

    2015-12-01

    This paper presents an AC-excited argon discharge generated using a gas-liquid (two-phase) hybrid plasma reactor, which mainly consists of a powered needle electrode enclosed in a conical quartz tube and grounded deionized water electrode. The discharges in the gas-phase, as well as in the two-phase, exhibit two discharge modes, i.e., the low current glow-like diffuse mode and the high current streamer-like constrict mode, with a mode transition, which exhibits a negative resistance of the discharges. The optical emission spectral analysis shows that the stronger diffusion of the water vapor into the discharge region in the two-phase discharges boosts up the generation of OH (A-X) radicals, and consequently, leads to a higher rotational temperature in the water-phase plasma plume than that of the gas-phase discharges. Both the increase of the power input and the decrease of the argon flow rate result in the increase of the rotational temperature in the plasma plume of the water-phase discharge. The stable two-phase discharges with a long plasma plume in the water-phase under a low power input and gas flow rate may show a promising prospect for the degradation of organic pollutants, e.g., printing and dyeing wastewater, in the field of environmental protection.

  6. Complex Organic Molecules Formation in Space Through Gas Phase Reactions: A Theoretical Approach

    Science.gov (United States)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2017-02-01

    Chemistry in the interstellar medium (ISM) is capable of producing complex organic molecules (COMs) of great importance to astrobiology. Gas phase and grain surface chemistry almost certainly both contribute to COM formation. Amino acids as building blocks of proteins are some of the most interesting COMs. The simplest one, glycine, has been characterized in meteorites and comets and, its conclusive detection in the ISM seems to be highly plausible. In this work, we analyze the gas phase reaction of glycine and {{{CH}}5}+ to establish the role of this process in the formation of alanine or other COMs in the ISM. Formation of protonated α- and β-alanine in spite of being exothermic processes is not viable under interstellar conditions because the different paths leading to these isomers present net activation energies. Nevertheless, glycine can evolve to protonated 1-imide-2, 2-propanediol, protonated amino acetone, protonated hydroxyacetone, and protonated propionic acid. However, formation of acetic acid and protonated methylamine is also a favorable process and therefore will be a competitive channel with the evolution of glycine to COMs.

  7. Probing Vitamine C, Aspirin and Paracetamol in the Gas Phase: High Resolution Rotational Studies

    Science.gov (United States)

    Mata, S.; Cabezas, C.; Varela, M.; Pena, I.; Nino, A.; López, J. C.; Alonso, J. L.; Grabow, J.-U.

    2011-06-01

    A solid sample of Vitamin C (m.p. 190°C) vaporized by laser ablation has been investigated in gas phase and characterized through their rotational spectra. Two spectroscopy techniques has been used to obtain the spectra: a new design of broadband chirped pulse Fourier transform microwave spectroscopy with in-phase/quadrature-phase-modulation passage-acquired-coherence technique (IMPACT) and conventional laser ablation molecular beam Fourier transform microwave spectroscopy (LA-MB-FTMW). Up to now, two low-energy conformer have been observed and their rotational constants determined. Ab initio calculations at the MP2/6-311++G (d,p) level of theory predicted rotational constants which helped us to identify these conformers unequivocally. Among the molecules to benefit from the LA-MB-FTMW technique there are common important drugs never observed in the gas phase through rotational spectroscopy. We present here the results on acetyl salicylic acid and acetaminophen (m.p. 136°C), commonly known as aspirin and paracetamol respectively. We have observed two stable conformers of aspirin and two for paracetamol. The internal rotation barrier of the methyl group in aspirin has been determined for both conformers from the analysis of the A-E splittings due to the coupling of internal and overall rotation. J. L. Alonso, C. Pérez, M. E. Sanz, J. C. López, S. Blanco, Phys. Chem. Chem. Phys. 11,617-627 (2009)and references therein

  8. NON-INTRUSIVE GAS-PHASE THERMOMETRY FOR INDUSTRIAL OXY-FUEL BURNERS

    Directory of Open Access Journals (Sweden)

    J. W. Tröger

    2015-03-01

    Full Text Available The use of oxy-fuel combustion processes is of large interest for several industrial fields applications since it offers the advantages of low NOx emissions in combination with high combustion temperatures even without additional preheating. For optimization of such processеs a detailed understanding based on precise experimental data is necessary. So far there is still a lack of precise experimental data achieved with high spatial and temporal resolution from industrial relevant turbulent oxy-fuel combustion processes. Beside species concentration information the gas phase temperature is of utmost importance for an improved understanding of the basic chemical reactions and the pollutant formation. The coherent anti-Stokes Raman spectroscopy (CARS technique is a very well suited laser based tool for a non-intrusive investigation of such turbulent high temperature combustion processes. In this work we analysed an industrial 400 kW oxy-fuel burner with the help of O2 based vibrational CARS system which is integrated in an industrial relevant test furnace. The burner is fed with pure oxygen and natural gas at an equivalence ratio of =0.9. At one downstream position temporal and spatial resolved temperatures were measured along a 600 mm line. Additional air sucked in from the environment seems to influence the gas phase temperature significantly.

  9. Supramolecular Adducts of Cucurbit[7]uril and Amino Acids in the Gas Phase

    Science.gov (United States)

    Kovalenko, Ekaterina; Vilaseca, Marta; Díaz-Lobo, Mireia; Masliy, A. N.; Vicent, Cristian; Fedin, Vladimir P.

    2016-02-01

    The complexation of the macrocyclic cavitand cucurbit[7]uril (Q7) with a series of amino acids (AA) with different side chains (Asp, Asn, Gln, Ser, Ala, Val, and Ile) is investigated by ESI-MS techniques. The 1:1 [Q7 + AA + 2H]2+ adducts are observed as the base peak when equimolar Q7:AA solutions are electrosprayed, whereas the 1:2 [Q7 + 2AA + 2H]2+ dications are dominant when an excess of the amino acid is used. A combination of ion mobility mass spectrometry (IM-MS) and DFT calculations of the 1:1 [Q7 + AA + 2H]2+ (AA = Tyr, Val, and Ser) adducts is also reported and proven to be unsuccessful at discriminating between exclusion or inclusion-type conformations in the gas phase. Collision induced dissociation (CID) revealed that the preferred dissociation pathways of the 1:1 [Q7 + AA + 2H]2+ dications are strongly influenced by the identity of the amino acid side chain, whereas ion molecule reactions towards N-butylmethylamine displayed a common reactivity pattern comprising AA displacement. Special emphasis is given on the differences between the gas-phase behavior of the supramolecular adducts with amino acids (AA = Asp, Asn, Gln, Ser, Ala, Val, and Ile) and those featuring basic (Lys and Arg) and aromatic (Tyr and Phe) side chains.

  10. Molecular dynamics simulation of gas-phase ozone reactions with sabinene and benzene.

    Science.gov (United States)

    Ridgway, H F; Mohan, B; Cui, X; Chua, K J; Islam, M R

    2017-06-01

    Gas-phase reactions of ozone (O3) with volatile organic compounds were investigated both by experiment and molecular simulations. From our experiments, it was found ozone readily reacts with VOC pure components and reduces it effectively. By introducing ozone intermittently, the reaction between VOC and ozone is markedly enhanced. In order to understand the relationship between intermediate reactions and end products, ozone reaction with benzene and alicyclic monoterpene sabinene were simulated via a novel hybrid quantum mechanical/molecular mechanics (QM/MM) algorithm that forced repeated bimolecular collisions. Molecular orbital (MO) rearrangements (manifested as bond dissociation or formation), resulting from the collisions, were computed by semi-empirical unrestricted Hartree-Fock methods (e.g., RM1). A minimum of 975 collisions between ozone and targeted organic species were performed to generate a distribution of reaction products. Results indicated that benzene and sabinene reacted with ozone to produce a range of stable products and intermediates, including carbocations, ring-scission products, as well as peroxy (HO2 and HO3) and hydroxyl (OH) radicals. Among the stable sabinene products observed included formaldehyde and sabina-ketone, which have been experimentally demonstrated in gas-phase ozonation reactions. Among the benzene ozonation products detected composed of oxygen mono-substituted aromatic C6H5O, which may undergo further transformation or rearrangement to phenol, benzene oxide or 2,4-cyclohexadienone; a phenomenon which has been experimentally observed in vapor-phase photocatalytic ozonation reactions. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. The effect of multilayer ice chemistry on gas-phase deuteration in starless cores

    CERN Document Server

    Sipilä, O; Taquet, V

    2016-01-01

    Aims. We aim to investigate whether a multilayer ice model can be as successful as a bulk ice model in reproducing the observed abundances of various deuterated gas-phase species toward starless cores. Methods. We calculate abundances for various deuterated species as functions of time adopting fixed physical conditions. We also estimate abundance gradients by adopting a modified Bonnor-Ebert sphere as a core model. In the multilayer ice scenario, we consider desorption from one or several monolayers on the surface. Results. We find that the multilayer model predicts abundances of $\\rm DCO^+$ and $\\rm N_2D^+$ that are about an order of magnitude lower than observed, caused by the trapping of CO and $\\rm N_2$ into the grain mantle. As a result of the mantle trapping, deuteration efficiency in the gas phase increases and we find stronger deuterium fractionation in ammonia than what has been observed. Another distinguishing feature of the multilayer model is that $\\rm D_3^+$ becomes the main deuterated ion at hi...

  12. Bacteria and fungi inactivation by photocatalysis under UVA irradiation: liquid and gas phase.

    Science.gov (United States)

    Rodrigues-Silva, Caio; Miranda, Sandra M; Lopes, Filipe V S; Silva, Mário; Dezotti, Márcia; Silva, Adrián M T; Faria, Joaquim L; Boaventura, Rui A R; Vilar, Vítor J P; Pinto, Eugénia

    2017-03-01

    In the last decade, environmental risks associated with wastewater treatment plants (WWTPs) have become a concern in the scientific community due to the absence of specific legislation governing the occupational exposure limits (OEL) for microorganisms present in indoor air. Thus, it is necessary to develop techniques to effectively inactivate microorganisms present in the air of WWTPs facilities. In the present work, ultraviolet light A radiation was used as inactivation tool. The microbial population was not visibly reduced in the bioaerosol by ultraviolet light A (UVA) photolysis. The UVA photocatalytic process for the inactivation of microorganisms (bacteria and fungi, ATCC strains and isolates from indoor air samples of a WWTP) using titanium dioxide (TiO2 P25) and zinc oxide (ZnO) was tested in both liquid-phase and airborne conditions. In the slurry conditions at liquid phase, P25 showed a better performance in inactivation. For this reason, gas-phase assays were performed in a tubular photoreactor packed with cellulose acetate monolithic structures coated with P25. The survival rate of microorganisms under study decreased with the catalyst load and the UVA exposure time. Inactivation of fungi was slower than resistant bacteria, followed by Gram-positive bacteria and Gram-negative bacteria. Graphical abstract Inactivation of fungi and bacteria in gas phase by photocatalitic process performed in a tubular photoreactor packed with cellulose acetate monolith structures coated with TiO2.

  13. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    Science.gov (United States)

    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 (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.

  14. Fourier transform infrared spectroscopy and theoretical study of dimethylamine dimer in the gas phase.

    Science.gov (United States)

    Du, Lin; Kjaergaard, Henrik G

    2011-11-10

    Dimethylamine (DMA) has been studied by gas-phase Fourier transform infrared (FTIR) spectroscopy. We have identified a spectral transition that is assigned to the DMA dimer. The IR spectra of the dimer in the gas phase are obtained by spectral subtraction of spectra recorded at different pressures. The enthalpy of hydrogen bond formation was obtained for the DMA dimer by temperature-dependence measurements. We complement the experimental results with ab initio and anharmonic local mode model calculations of monomer and dimer. Compared to the monomer, our calculations show that in the dimer the N-H bond is elongated, and the NH-stretching fundamental shifts to a lower wavenumber. More importantly, the weak NH-stretching fundamental transition has a pronounced intensity increase upon complexation. However, the first NH-stretching overtone transition is not favored by the same intensity enhancement, and we do not observe the first NH-stretching overtone of the dimer. On the basis of the measured and calculated intensity of the NH-stretching transition of the dimer, the equilibrium constant for dimerization at room temperature was determined.

  15. Gas-phase dehydration of glycerol over commercial Pt/γ-Al2O3 catalysts

    Institute of Scientific and Technical Information of China (English)

    Sergey Danov; Anton Esipovich; Artem Belousov; Anton Rogozhin

    2015-01-01

    Gas-phase dehydration of glycerol to produce acrolein was investigated over commercial catalysts based onγ-Al2O3, viz. A-64, A-56, I-62, AP-10, AP-56, AP-64 and KR-104. To understand the effect of Cl−anions, HCl-impregnated sup-ports have been investigated in the dehydration reaction of glycerol at 375 °C. For comparison, various H-zeolites were also examined. It was found that the glycerol conversion over the solid acid catalysts was strongly dependent on their acidity and surface area. And the relationship between the catalytic activity and the acidity of the catalysts was discussed. The outstanding properties of Pt/γ-Al2O3 catalyst systems for the dehydration of glycerol were revealed. Pt/γ-Al2O3 catalyst (AP-64) showed the highest catalytic activity after 50 h of reaction with an acrolein selectivity of 65%at a conversion of glycerol of 90%. Based on these results, catalysts based onγ-Al2O3 appear to be most promising for gas phase dehydration of glycerol.

  16. Incorporating the molecular gas phase in galaxy-size numerical simulations: first applications in dwarf galaxies

    CERN Document Server

    Pelupessy, F I; Van der Werf, P P

    2006-01-01

    We present models of the evolution of the gaseous and stellar content of galaxies incorporating the formation of H_2 out of HI gas as part of such a model. We do so by formulating a subgrid model for gas clouds that uses well-known cloud scaling relations and solves for the HI-H_2 balance set by the H_2 formation on dust grains and its FUV-induced photodissociation by the temporally and spatially varying interstellar radiation field. This allows the seamless tracking of the evolution of the H_2 gas phase, its precursor Cold Neutral Medium (CNM) HI gas, simultaneously with the star formation. Our most important findings are: a) a significant dependence of the HI-H_2 transition and the resultant H_2 gas mass on the ambient metallicity and the H_2 formation rate, b) the important influence of the characteristic star formation timescale (regulating the ambient FUV radiation field) on the equilibrium H_2 gas mass and c) the possibility of a diffuse H_2 gas phase. Finally, we implement and briefly explore a novel a...

  17. Graphene quantum dots modified silicon nanowire array for ultrasensitive detection in the gas phase

    Science.gov (United States)

    Li, T. Y.; Duan, C. Y.; Zhu, Y. X.; Chen, Y. F.; Wang, Y.

    2017-03-01

    Si nanostructure-based gas detectors have attracted much attention due to their huge surface areas, relatively high carrier mobility, maneuverability for surface functionalization and compatibility to modern electronic industry. However, the unstable surface of Si, especially for the nanostructures in a corrosive atmosphere, hinders their sensitivity and reproducibility when used for detection in the gas phase. In this study, we proposed a novel strategy to fabricate a Si-based gas detector by using the vertically aligned Si nanowire (SiNW) array as a skeleton and platform, and decorated chemically inert graphene quantum dots (GQDs) to protect the SiNWs from oxidation and promote the carriers’ interaction with the analytes. The radial core–shell structures of the GQDs/SiNW array were then assembled into a resistor-based gas detection system and evaluated by using nitrogen dioxide (NO2) as the model analyte. Compared to the bare SiNW array, our novel sensor exhibited ultrahigh sensitivity for detecting trace amounts of NO2 with the concentration as low as 10 ppm in room temperature and an immensely reduced recovery time, which is of significant importance for their practical application. Meanwhile, strikingly, reproducibility and stability could also be achieved by showing no sensitivity decline after storing the GQDs/SiNW array in air for two weeks. Our results demonstrate that protecting the surface of the SiNW array with chemically inert GQDs is a feasible strategy to realize ultrasensitive detection in the gas phase.

  18. Inclusion complexes of ionic liquids and cyclodextrins: are they formed in the gas phase?

    Science.gov (United States)

    Fernandes, Ana M; Schröder, Bernd; Barata, Tânia; Freire, Mara G; Coutinho, João A P

    2014-05-01

    The interaction of imidazolium-based ionic liquids with α- and β-cyclodextrins was investigated by electrospray ionization mass spectrometry with variable collision induced dissociation energy and quantum chemical gas-phase calculations. The center-of-mass energy at which 50% of a precursor ion decomposes (Ecm,1/2) was determined for the isolated [cyclodextrin + cation](+) or [cyclodextrin + anion](-) adduct ions of imidazolium-based ionic liquids with different alkyl chain lengths combined with a large set of anions, such as chloride, bromide, bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, methanesulfonate, dicyanamide, and hydrogensulfate. Moreover, both symmetric and asymmetric imidazolium cationic cores were evaluated. The relative interaction energies in the adduct ions were interpreted in terms of the influence of cation/anion structures and their inherent properties, such as hydrophobicity and hydrogen bond accepting ability, in the complexation process with the cyclodextrins. The trends observed in the mass spectral data together with quantum-chemical calculations suggest that in the gas phase, cations and anions will preferentially interact with the lower or upper rim of the cyclodextrin, respectively, as opposed to what has been reported in condensed phase where the formation of an inclusion complex between ionic liquid and cyclodextrin is assumed.

  19. TRANSITION STATE FOR THE GAS-PHASE REACTION OF URANIUM HEXAFLUORIDE WITH WATER

    Energy Technology Data Exchange (ETDEWEB)

    Garrison, S; James Becnel, J

    2008-03-18

    Density Functional Theory and small-core, relativistic pseudopotentials were used to look for symmetric and asymmetric transitions states of the gas-phase hydrolysis reaction of uranium hexafluoride, UF{sub 6}, with water. At the B3LYP/6-31G(d,p)/SDD level, an asymmetric transition state leading to the formation of a uranium hydroxyl fluoride, U(OH)F{sub 5}, and hydrogen fluoride was found with an energy barrier of +77.3 kJ/mol and an enthalpy of reaction of +63.0 kJ/mol (both including zero-point energy corrections). Addition of diffuse functions to all atoms except uranium led to only minor changes in the structure and relative energies of the reacting complex and transition state. However, a significant change in the product complex structure was found, significantly reducing the enthalpy of reaction to +31.9 kJ/mol. Similar structures and values were found for PBE0 and MP2 calculations with this larger basis set, supporting the B3LYP results. No symmetric transition state leading to the direct formation of uranium oxide tetrafluoride, UOF{sub 4}, was found, indicating that the reaction under ambient conditions likely includes several more steps than the mechanisms commonly mentioned. The transition state presented here appears to be the first published transition state for the important gas-phase reaction of UF{sub 6} with water.

  20. Comparison of electrical and optical characteristics in gas-phase and gas-liquid phase discharges

    Energy Technology Data Exchange (ETDEWEB)

    Qazi, H. I. A.; Li, He-Ping, E-mail: liheping@tsinghua.edu.cn; Zhang, Xiao-Fei; Bao, Cheng-Yu [Department of Engineering Physics, Tsinghua University, Beijing 100084 (China); Nie, Qiu-Yue [School of Electrical Engineering and Automation, Harbin Institute of Technology, Harbin, Heilongjiang Province 150001 (China)

    2015-12-15

    This paper presents an AC-excited argon discharge generated using a gas-liquid (two-phase) hybrid plasma reactor, which mainly consists of a powered needle electrode enclosed in a conical quartz tube and grounded deionized water electrode. The discharges in the gas-phase, as well as in the two-phase, exhibit two discharge modes, i.e., the low current glow-like diffuse mode and the high current streamer-like constrict mode, with a mode transition, which exhibits a negative resistance of the discharges. The optical emission spectral analysis shows that the stronger diffusion of the water vapor into the discharge region in the two-phase discharges boosts up the generation of OH (A–X) radicals, and consequently, leads to a higher rotational temperature in the water-phase plasma plume than that of the gas-phase discharges. Both the increase of the power input and the decrease of the argon flow rate result in the increase of the rotational temperature in the plasma plume of the water-phase discharge. The stable two-phase discharges with a long plasma plume in the water-phase under a low power input and gas flow rate may show a promising prospect for the degradation of organic pollutants, e.g., printing and dyeing wastewater, in the field of environmental protection.

  1. Encapsulating Cytochrome c in Silica Aerogel Nanoarchitectures without Metal Nanoparticles while Retaining Gas-phase Bioactivity

    Science.gov (United States)

    Harper-Leatherman, Amanda S.; Pacer, Elizabeth R.; Kosciuszek, Nina D.

    2016-01-01

    Applications such as sensors, batteries, and fuel cells have been improved through the use of highly porous aerogels when functional compounds are encapsulated within the aerogels. However, few reports on encapsulating proteins within sol–gels that are processed to form aerogels exist. A procedure for encapsulating cytochrome c (cyt. c) in silica (SiO2) sol-gels that are supercritically processed to form bioaerogels with gas-phase activity for nitric oxide (NO) is presented. Cyt. c is added to a mixed silica sol under controlled protein concentration and buffer strength conditions. The sol mixture is then gelled and the liquid filling the gel pores is replaced through a series of solvent exchanges with liquid carbon dioxide. The carbon dioxide is brought to its critical point and vented off to form dry aerogels with cyt. c encapsulated inside. These bioaerogels are characterized with UV-visible spectroscopy and circular dichroism spectroscopy and can be used to detect the presence of gas-phase nitric oxide. The success of this procedure depends on regulating the cyt. c concentration and the buffer concentration and does not require other components such as metal nanoparticles. It may be possible to encapsulate other proteins using a similar approach making this procedure important for potential future bioanalytical device development. PMID:26967257

  2. Oxidation of methionine residues in polypeptide ions via gas-phase ion/ion chemistry.

    Science.gov (United States)

    Pilo, Alice L; McLuckey, Scott A

    2014-06-01

    The gas-phase oxidation of methionine residues is demonstrated here using ion/ion reactions with periodate anions. Periodate anions are observed to attach in varying degrees to all polypeptide ions irrespective of amino acid composition. Direct proton transfer yielding a charge-reduced peptide ion is also observed. In the case of methionine and, to a much lesser degree, tryptophan-containing peptide ions, collisional activation of the complex ion generated by periodate attachment yields an oxidized peptide product (i.e., [M + H + O](+)), in addition to periodic acid detachment. Detachment of periodic acid takes place exclusively for peptides that do not contain either a methionine or tryptophan side chain. In the case of methionine-containing peptides, the [M + H + O](+) product is observed at a much greater abundance than the proton transfer product (viz., [M + H](+)). Collisional activation of oxidized Met-containing peptides yields a signature loss of 64 Da from the precursor and/or product ions. This unique loss corresponds to the ejection of methanesulfenic acid from the oxidized methionine side chain and is commonly used in solution-phase proteomics studies to determine the presence of oxidized methionine residues. The present work shows that periodate anions can be used to 'label' methionine residues in polypeptides in the gas phase. The selectivity of the periodate anion for the methionine side chain suggests several applications including identification and location of methionine residues in sequencing applications.

  3. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    CERN Document Server

    Rondo, L.; 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

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosolnucleation. Based on quantum chemical calculations it has been suggested that the quantitative detectionof gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased inthe presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was setup at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection ofH2SO4in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time inthe 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, neutralsulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presenceof dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS...

  4. Native like helices in a specially designed β peptide in the gas phase.

    Science.gov (United States)

    Schubert, Franziska; Pagel, Kevin; Rossi, Mariana; Warnke, Stephan; Salwiczek, Mario; Koksch, Beate; von Helden, Gert; Blum, Volker; Baldauf, Carsten; Scheffler, Matthias

    2015-02-21

    In the natural peptides, helices are stabilized by hydrogen bonds that point backward along the sequence direction. Until now, there is only little evidence for the existence of analogous structures in oligomers of conformationally unrestricted β amino acids. We specifically designed the β peptide Ac-(β(2)hAla)6-LysH(+) to form native like helical structures in the gas phase. The design follows the known properties of the peptide Ac-Ala6-LysH(+) that forms a α helix in isolation. We perform ion-mobility mass-spectrometry and vibrational spectroscopy in the gas phase, combined with state-of-the-art density-functional theory simulations of these molecular systems in order to characterize their structure. We can show that the straightforward exchange of alanine residues for the homologous β amino acids generates a system that is generally capable of adopting native like helices with backward oriented H-bonds. By pushing the limits of theory and experiments, we show that one cannot assign a single preferred structure type due to the densely populated energy landscape and present an interpretation of the data that suggests an equilibrium of three helical structures.

  5. Carbonyl Compounds in the Gas Phase of Cigarette Mainstream Smoke and Their Pharmacological Properties.

    Science.gov (United States)

    Horinouchi, Takahiro; Higashi, Tsunehito; Mazaki, Yuichi; Miwa, Soichi

    2016-01-01

    Cigarette mainstream smoke is composed of gas and tar phases and contains >4000 chemical constituents, including nicotine and tar. The substances in the gas phase but not in the tar phase can pass through the airway epithelial barrier, enter the systemic circulation via the pulmonary circulation, and increase systemic oxidative damage, leading to the development of cigarette smoking-related diseases such as atherosclerosis. Recently, we identified some stable carbonyl compounds, including acrolein (ACR) and methyl vinyl ketone (MVK), as major cytotoxic factors in nicotine- and tar-free cigarette smoke extract (CSE) of the gas phase. CSE, ACR, and MVK induce protein kinase C (PKC)-dependent activation of reduced nicotinamide adenine dinucleotide phosphate (NADPH) oxidase (NOX) and subsequent generation of reactive oxygen species (ROS) via NOX, causing plasma membrane damage and cell apoptosis. CSE, ACR, and MVK also trigger carbonylation of PKC, which is an irreversible oxidative modification. Cell damage and PKC carbonylation in response to treatment with CSE, ACR, or MVK are abolished by thiol-containing antioxidants such as N-acetyl-L-cysteine and reduced glutathione. Thus pharmacological modulation of PKC and NOX activities and the trapping of ROS are potential strategies for the prevention of diseases related to cigarette smoking.

  6. Gas-phase pesticide measurement using iodide ionization time-of-flight mass spectrometry

    Directory of Open Access Journals (Sweden)

    T. Murschell

    2017-06-01

    Full Text Available Volatilization and subsequent processing in the atmosphere are an important environmental pathway for the transport and chemical fate of pesticides. However, these processes remain a particularly poorly understood component of pesticide lifecycles due to analytical challenges in measuring pesticides in the atmosphere. Most pesticide measurements require long (hours to days sampling times coupled with offline analysis, inhibiting observation of meteorologically driven events or investigation of rapid oxidation chemistry. Here, we present chemical ionization time-of-flight mass spectrometry with iodide reagent ions as a fast and sensitive measurement of four current-use pesticides. These semi-volatile pesticides were calibrated with injections of solutions onto a filter and subsequently volatilized to generate gas-phase analytes. Trifluralin and atrazine are detected as iodide–molecule adducts, while permethrin and metolachlor are detected as adducts between iodide and fragments of the parent analyte molecule. Limits of detection (1 s are 0.37, 0.67, 0.56, and 1.1 µg m−3 for gas-phase trifluralin, metolachlor, atrazine, and permethrin, respectively. The sensitivities of trifluralin and metolachlor depend on relative humidity, changing as much as 70 and 59, respectively, as relative humidity of the sample air varies from 0 to 80 %. This measurement approach is thus appropriate for laboratory experiments and potentially near-source field measurements.

  7. Liquid-gas phase transition in strange hadronic matter with relativistic models

    Science.gov (United States)

    Torres, James R.; Gulminelli, F.; Menezes, Débora P.

    2016-02-01

    Background: The advent of new dedicated experimental programs on hyperon physics is rapidly boosting the field, and the possibility of synthesizing multiple strange hypernuclei requires the addition of the strangeness degree of freedom to the models dedicated to nuclear structure and nuclear matter studies at low energy. Purpose: We want to settle the influence of strangeness on the nuclear liquid-gas phase transition. Because of the large uncertainties concerning the hyperon sector, we do not aim at a quantitative estimation of the phase diagram but rather at a qualitative description of the phenomenology, as model independent as possible. Method: We analyze the phase diagram of low-density matter composed of neutrons, protons, and Λ hyperons using a relativistic mean field (RMF) model. We largely explore the parameter space to pin down generic features of the phase transition, and compare the results to ab initio quantum Monte Carlo calculations. Results: We show that the liquid-gas phase transition is only slightly quenched by the addition of hyperons. Strangeness is seen to be an order parameter of the phase transition, meaning that dilute strange matter is expected to be unstable with respect to the formation of hyperclusters. Conclusions: More quantitative results within the RMF model need improved functionals at low density, possibly fitted to ab initio calculations of nuclear and Λ matter.

  8. Synchrotron and small bio-molecules in gas phase and liquid environment: new opportunities in Brazil

    Energy Technology Data Exchange (ETDEWEB)

    Naves de Brito, A. [State University of Campinas (UNICAMP), SP (Brazil). Dept. of Applied Physics

    2011-07-01

    Full text: Two techniques are critically related to the photoelectric law, namely: photoelectron spectroscopy and photoelectron-photoion coincidence spectroscopy. Both are strongly used now a day within synchrotron laboratories. Our group is employing both to investigate fragmentation of bio-molecules in gas phase such as amino acids and DNA basis using V UV and soft x-ray photons. In the near future lager scale instruments developed in Brazil will allow unique opportunities to apply these two spectroscopic methods to molecules immersed in liquids such as water. We will present details from this advanced x-ray source and experimental stations with capabilities not present in other places in the world. Experiments connected to the molecular origin of live will be shown. Among them an experiment where we mimic the atmosphere at Titan moon producing bio- molecules will discussed. Another experiment will be presented where we test the Panspermia viability using special bacteria. We will also present experiments where frozen simple molecules connected to pre-biotic mate- rial are bombardment by UV photons and energetic particles showing interesting trends. Spectroscopic studies of gas phase photo-fragmentation of bio-molecules may be critical to understand in the future these molecules immersed in liquids. We plan to spend some time showing our recent results in this area. (author)

  9. Reactive species output of a plasma jet with a shielding gas device—combination of FTIR absorption spectroscopy and gas phase modelling

    Science.gov (United States)

    Schmidt-Bleker, A.; Winter, J.; Iseni, S.; Dünnbier, M.; Weltmann, K.-D.; Reuter, S.

    2014-04-01

    In this work, a simple modelling approach combined with absorption spectroscopy of long living species generated by a cold atmospheric plasma jet yields insight into relevant gas phase chemistry. The reactive species output of the plasma jet is controlled using a shielding gas device. The shielding gas is varied using mixtures of oxygen and nitrogen at various humidity levels. Through the combination of Fourier transform infrared (FTIR) spectroscopy, computational fluid dynamics (CFD) simulations and zero dimensional kinetic modelling of the gas phase chemistry, insight into the underlying reaction mechanisms is gained. While the FTIR measurements yield absolute densities of ozone and nitrogen dioxide in the far field of the jet, the kinetic simulations give additional information on reaction pathways. The simulation is fitted to the experimentally obtained data, using the CFD simulations of the experimental setup to estimate the correct evaluation time for the kinetic simulation. It is shown that the ozone production of the plasma jet continuously rises with the oxygen content in the shielding gas, while it significantly drops as humidity is increased. The production of nitrogen dioxide reaches its maximum at about 30% oxygen content in the shielding gas. The underlying mechanisms are discussed based on the simulation results.

  10. Atmospheric measurements of gas-phase HNO3 and SO2 using chemical ionization mass spectrometry during the MINATROC field campaign 2000 on Monte Cimone

    Directory of Open Access Journals (Sweden)

    M. Hanke

    2003-01-01

    Full Text Available The EU-project MINATROC (MINeral dust And TROpospheric Chemistry aims at enabling an estimation of the influence of mineral dust, a major, but to date largely ignored component of tropospheric aerosol, on tropospheric oxidant cycles. Within the scope of this project continuous atmospheric measurements of gas-phase HNO3 and SO2 were conducted in June and July 2000 at the CNR WMO station, situated on Monte Cimone (MTC (44°11' N --10°42' E, 2165 m asl, Italy. African air transporting dust is occasionally advected over the Mediterranean Sea to the site, thus mineral aerosol emitted from Africa will encounter polluted air masses and provide ideal conditions to study their interactions. HNO3 and SO2 were measured with an improved CIMS (chemical ionization mass spectrometry system for ground-based measurements that was developed and built at MPI-K Heidelberg. Since HNO3  is a very sticky compound special care was paid for the air-sampling and background-measurement system. Complete data sets could be obtained before, during and after major dust intrusions. For the first time these measurements might provide a strong observational indication of efficient uptake of gas-phase HNO3 by atmospheric mineral-dust aerosol particles.

  11. Comprehensive Analysis of Interstellar Iso-PROPYL Cyanide up to 480 GHZ

    Science.gov (United States)

    Kolesniková, Lucie; Alonso, E. R.; Cabezas, Carlos; Mata, Santiago; Alonso, José L.

    2016-06-01

    Iso-propyl cyanide, also known as iso-butyronitrile, is a branched alkyl molecule recently detected in the interstellar medium. A combination of Stark-modulated microwave spectroscopy and frequency-modulated millimeter and submillimeter wave spectroscopy was used to analyze its rotational spectrum from 26 to 480 GHz. Spectral assignments and analysis include transitions from the ground state, eight excited vibrational states and 13C isotopologues. Results of this work should facilitate astronomers further observations of iso-propyl cyanide in the interstellar medium. A. Belloche, R. T. Garrod, H. S. P. Müller, K. M. Menten, Science, 2014, 345, 1584

  12. X-ray diffraction investigation of 1-phenyl-3-isopropyl-5-(benzothiazol-2-yl)formazan

    Science.gov (United States)

    Slepukhin, P. A.; Pervova, I. G.; Rezinskikh, Z. G.; Lipunova, G. N.; Gorbatenko, Yu. A.; Lipunov, I. N.

    2008-01-01

    The crystal structure of 1-phenyl-3-isopropyl-5-(benzothiazol-2-yl)formazan is investigated using X-ray diffraction. The compound crystallizes in the form of two crystallographically independent molecules ( A and B) in identical conformations that are stabilized by intermolecular hydrogen bonds. The intermolecular hydrogen bonds N-H…N (N…N, 2.892 and 2.939 Å) link molecules into AB dimers. Both molecules have a flattened structure, except for the isopropyl fragment. The bonds in the formazan chains are delocalized. Molecules A and B have close geometric characteristics.

  13. 21 CFR 177.2280 - 4,4′-Isopropyl-idenedi-phenol-epichloro-hydrin thermo-setting epoxy resins.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true 4,4â²-Isopropyl-idenedi-phenol-epichloro-hydrin thermo-setting epoxy resins. 177.2280 Section 177.2280 Food and Drugs FOOD AND DRUG ADMINISTRATION...,4′-Isopropyl-idenedi-phenol-epichloro-hydrin thermo-setting epoxy resins....

  14. Comparing the gas-phase fragmentation reactions of protonated and radical cations of the tripeptides GXR

    Science.gov (United States)

    Wee, Sheena; O'Hair, Richard A. J.; McFadyen, W. David

    2004-05-01

    Electrospray ionization (ESI) mass spectrometry of methanolic solutions of mixtures of the copper salt (2,2':6',2''-terpyridine)copper(II) nitrate monohydrate ([Cu(II)(tpy)(NO3)2].H2O) and a tripeptide GXR (where X = 1 of the 20 naturally occurring amino acids) yielded [Cu(II)(tpy)(GXR)][radical sign]2+ ions, which were then subjected to collision induced dissociation (CID). In all but one case (GRR), these [Cu(II)(tpy)(GXR)][radical sign]2+ ions fragment to form odd electron GXR[radical sign]+ radical cations with sufficient abundance to examine their gas-phase fragmentation reactions. The GXR[radical sign]+ radical cations undergo a diverse range of fragmentation reactions which depend on the nature of the side chain of X. Many of these reactions can be rationalized as arising from the intermediacy of isomeric distonic ions in which the charge (i.e. proton) is sequestered by the highly basic arginine side chain and the radical site is located at various positions on the tripeptide including the peptide back bone and side chains. The radical sites in these distonic ions often direct the fragmentation reactions via the expulsion of small radicals (to yield even electron ions) or small neutrals (to form radical cations). Both classes of reaction can yield useful structural information, allowing for example, distinction between leucine and isoleucine residues. The gas-phase fragmentation reactions of the GXR[radical sign]+ radical cations are also compared to their even electron [GXR+H]+ and [GXR+2H]2+ counterparts. The [GXR+H]+ ions give fewer sequence ions and more small molecule losses while the [GXR+2H]2+ ions yield more sequence information, consistent with the [`]mobile proton model' described in previous studies. In general, all three classes of ions give complementary structural information, but the GXR[radical sign]+ radical cations exhibit a more diverse loss of small species (radicals and neutrals). Finally, links between these gas-phase results and key

  15. Far-Ir Spectroscopy of Neutral Gas Phase Peptides: Signatures from Combined Experiments and Simulations

    Science.gov (United States)

    Mahé, Jérôme; Gaigeot, Marie-Pierre; Bakker, Daniël; Jaeqx, Sander; Rijs, Anouk

    2016-06-01

    Within the past two decades, action vibrational spectroscopy has become an almost routine experimental method to probe the structures of molecules and clusters in the gas phase (neutral and ions). Such experiments are mainly performed in the 1000-4000 wn fingerprint regions. Though successful in many respects, these spectral domains can be however restrictive in the information provided, and sometimes reach limitations for unravelling structures without ambiguity. In a collaborative work with the group of Dr A.M. Rijs (FELIX laboratory, Radbout University, The Netherlands) we have launched a new strategy where the far-IR/Tera-Hertz domain (100-800 wn domain) is experimentally probed for neutral gas phase molecules. Our group in Paris apply finite temperature DFT-based molecular dynamics (DFT-MD) simulations in order to unravel the complex signatures arising in the far-IR domain, and provide an unambiguous assignment both of the structural conformation of the gas phase molecules (taking into account the experimental conditions) and an understanding of the spectral signatures/fingerprints. We will discuss our experimental and theoretical investigations on two neutral peptides in the 100-800 wn far-IR spectral domain, i.e. Z-Ala6 and PheGly dipeptide, that represent two systems which definitive conformational assignment was not possible without the far IR signatures. We will also present our very recent results on the Phe-X peptide series, where X stands for Gly, Ala, Pro, Val, Ser, Cys, combining experiments and DFT-MD simulations, providing a detailed understanding of the vibrational fingerprints in the far-IR domain. In all exemples, we will show how DFT-MD simulations is the proper theoretical tool to account for vibrational anharmonicities and mode couplings, of prime importance in the far-IR domain. References : J. Mahé, S. Jaeqx, A.M. Rijs, M.P. Gaigeot, Phys. Chem. Chem. Phys., 17 :25905 (2015) S. Jaeqx, J. Oomens, A. Cimas, M.P. Gaigeot, A.M. Rijs, Angew

  16. Nitric oxide gas phase release in human small airway epithelial cells

    Directory of Open Access Journals (Sweden)

    Suresh Vinod

    2009-01-01

    Full Text Available Abstract Background Asthma is a chronic airway inflammatory disease characterized by an imbalance in both Th1 and Th2 cytokines. Exhaled nitric oxide (NO is elevated in asthma, and is a potentially useful non-invasive marker of airway inflammation. However, the origin and underlying mechanisms of intersubject variability of exhaled NO are not yet fully understood. We have previously described NO gas phase release from normal human bronchial epithelial cells (NHBEs, tracheal origin. However, smaller airways are the major site of morbidity in asthma. We hypothesized that IL-13 or cytomix (IL-1β, TNF-α, and IFN-γ stimulation of differentiated small airway epithelial cells (SAECs, generation 10–12 and A549 cells (model cell line of alveolar type II cells in culture would enhance NO gas phase release. Methods Confluent monolayers of SAECs and A549 cells were cultured in Transwell plates and SAECs were allowed to differentiate into ciliated and mucus producing cells at an air-liquid interface. The cells were then stimulated with IL-13 (10 ng/mL or cytomix (10 ng/mL for each cytokine. Gas phase NO release in the headspace air over the cells was measured for 48 hours using a chemiluminescence analyzer. Results In contrast to our previous result in NHBE, baseline NO release from SAECs and A549 is negligible. However, NO release is significantly increased by cytomix (0.51 ± 0.18 and 0.29 ± 0.20 pl.s-1.cm-2, respectively reaching a peak at approximately 10 hours. iNOS protein expression increases in a consistent pattern both temporally and in magnitude. In contrast, IL-13 only modestly increases NO release in SAECs reaching a peak (0.06 ± 0.03 pl.s-1.cm-2 more slowly (30 to 48 hours, and does not alter NO release in A549 cells. Conclusion We conclude that the airway epithelium is a probable source of NO in the exhaled breath, and intersubject variability may be due, in part, to variability in the type (Th1 vs Th2 and location (large vs small airway

  17. Ultrafast electron diffraction from laser-aligned molecules in the gas phase

    Science.gov (United States)

    Yang, Jie

    Ultrafast electron diffraction has emerged since the end of last century, and has become an increasingly important tool for revealing great details of molecular dynamics. In comparison to spectroscopic techniques, ultrafast electron diffraction directly probes time-resolved structure of target molecules, and therefore can potentially provide "molecular movies" of the reactions being studied. These molecular movies are critical for understanding and ultimately controlling the energy conversion pathways and efficiencies of photochemical processes. In this dissertation, I have focused on ultrafast electron diffraction from gas-phase molecules, and have investigated several long-standing challenges that have been preventing researchers from being able to achieve 3-D molecular movies of photochemical reactions. The first challenge is to resolve the full 3-D structure for molecules in the gas phase. The random orientation of molecules in the gas phase smears out the diffraction signal, which results in only 1-D structural information being accessible. The second challenge lies in temporal resolution. In order to resolve coherent nuclear motions on their natural time scale, a temporal resolution of ˜200 femtosecond or better is required. However, due to experimental limitations the shortest temporal resolution that had been achieved was only a few picoseconds in early 2000, by Zewail group from Caltech. The first challenge is tackled by laser-alignment. In the first half of the dissertation, I approach this method both theoretically and experimentally, and demonstrate that by using a short laser pulse to transiently align target molecules in space, 3-D molecular structure can be reconstructed ab-initio from diffraction patterns. The second half of the dissertation presents two experiments, both of which are important steps toward imaging coherent nuclear motions in real time during photochemical reactions. The first experiment simultaneously resolves molecular alignment

  18. Gas-phase lithium cation basicity of histamine and its agonist 2-([beta]-aminoethyl)-pyridine

    Science.gov (United States)

    Hallmann, M.; Raczynska, E. D.; Gal, J. F.; Maria, P. C.

    2007-11-01

    The gas-phase lithium cation basicities (LCBs) were obtained for histamine (HA) and its agonist 2-([beta]-aminoethyl)-pyridine (AEP) from collision-induced dissociation of lithium adducts using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). For measurements, MeO(CH2)2OMe, Et3PO and (Me2N)3PO (HMPA) were used as the reference compounds. The experimental LCB of AEP was located between those of Et3PO and (Me2N)3PO. The experimental LCB of HA was found to be higher than those of AEP and HMPA by more than 2 kcal mol-1 clearly indicating that the LCB of HA is higher than any LCB for a neutral base yet measured (crown-ethers excepted). The experimental LCBs of the parent bases (pyridine and imidazole) are lower by more than 10 kcal mol-1. In parallel, DFT calculations {B3LYP/6-31G*//B3LYP/6-31G* and B3LYP/6-311+G**//B3LYP/6-31G*} were performed for HA, AEP and their lithium adducts. Among the 22 reasonable conformations of the HA-Li+ adduct, only one appears to be significantly more stable than the others. This is also the case for one structure among seven conformations of the AEP-Li+ adduct. These two stable structures have the [`]scorpion' conformation, in which the Li+ cation is almost equally chelated by two basic nitrogen atoms, the ring N-aza and the chain N-amino. Other HA-Li+ and AEP-Li+ conformations have noticeably higher energies than the [`]scorpion' structures. The difference between the DFT calculated LCBs of HA and AEP (about 4 kcal mol-1) is in agreement with that experimentally obtained (>2 kcal mol-1). The high experimental and theoretical values of LCB for HA and AEP militate in favor of a strong chelation of Li+ by both ligands in the gas-phase. This chelation effect was also evidenced previously for the proton gas-phase basicity.

  19. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup

    2015-08-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

  20. Heterogeneity-enhanced gas phase formation in shallow aquifers during leakage of CO2-saturated water from geologic sequestration sites

    Science.gov (United States)

    Plampin, Michael R.; Lassen, Rune N.; Sakaki, Toshihiro; Porter, Mark L.; Pawar, Rajesh J.; Jensen, Karsten H.; Illangasekare, Tissa H.

    2014-12-01

    A primary concern for geologic carbon storage is the potential for leakage of stored carbon dioxide (CO2) into the shallow subsurface where it could degrade the quality of groundwater and surface water. In order to predict and mitigate the potentially negative impacts of CO2 leakage, it is important to understand the physical processes that CO2 will undergo as it moves through naturally heterogeneous porous media formations. Previous studies have shown that heterogeneity can enhance the evolution of gas phase CO2 in some cases, but the conditions under which this occurs have not yet been quantitatively defined, nor tested through laboratory experiments. This study quantitatively investigates the effects of geologic heterogeneity on the process of gas phase CO2 evolution in shallow aquifers through an extensive set of experiments conducted in a column that was packed with layers of various test sands. Soil moisture sensors were utilized to observe the formation of gas phase near the porous media interfaces. Results indicate that the conditions under which heterogeneity controls gas phase evolution can be successfully predicted through analysis of simple parameters, including the dissolved CO2 concentration in the flowing water, the distance between the heterogeneity and the leakage location, and some fundamental properties of the porous media. Results also show that interfaces where a less permeable material overlies a more permeable material affect gas phase evolution more significantly than interfaces with the opposite layering.

  1. Multifunctional acid formation from the gas-phase ozonolysis of beta-pinene.

    Science.gov (United States)

    Ma, Yan; Marston, George

    2008-10-28

    The gas-phase ozonolysis of beta-pinene was studied in static chamber experiments, using gas chromatography coupled to mass spectrometric and flame ionisation detection to separate and detect products. A range of multifunctional organic acids-including pinic acid, norpinic acid, pinalic-3-acid, pinalic-4-acid, norpinalic acid and OH-pinalic acid-were identified in the condensed phase after derivatisation. Formation yields for these products under systematically varying reaction conditions (by adding different OH radical scavengers and Criegee intermediate scavengers) were investigated and compared with those observed from alpha-pinene ozonolysis, allowing detailed information on product formation mechanisms to be elucidated. In addition, branching ratios for the initial steps of the reaction were inferred from quantitative measurements of primary carbonyl formation. Atmospheric implications of this work are discussed.

  2. Cyclization of 1,4-hydroxycarbonyls is not a homogenous gas phase process

    Science.gov (United States)

    Dibble, Theodore S.

    2007-10-01

    Previous studies of 1,4-hydroxycarbonyls derived from alkanes have suggested that they can cyclize to saturated furans, which can subsequently eliminate water to form the corresponding dihydrofurans. CBS-QB3 and G3 studies of 5-hydroxy-2-pentanone and 2-hydroxypentanal show that both steps have activation barriers far too large for these reactions to occur as homogenous gas phase reactions. Similar results were obtained in CBS-QB3 studies of the analogous process leading from 2- and 3-methyl-4-hydroxy-2-butenal (species posited to form in the degradation of isoprene) to 3-methylfuran. The latter two processes are much more favorable, thermodynamically, than the formation of dihydrofurans from the saturated 1,4-hydroxycarbonyls.

  3. Exploring Systematic Effects in the Relation Between Stellar Mass, Gas Phase Metallicity, and Star Formation Rate

    CERN Document Server

    Telford, O Grace; Skillman, Evan D; Conroy, Charlie

    2016-01-01

    There is evidence that the well-established mass-metallicity relation in galaxies is correlated with a third parameter: star formation rate (SFR). The strength of this correlation may be used to disentangle the relative importance of different physical processes (e.g., infall of pristine gas, metal-enriched outflows) in governing chemical evolution. However, all three parameters are susceptible to biases that might affect the observed strength of the relation between them. We analyze possible sources of systematic error, including sample bias, application of S/N cuts on emission lines, choice of metallicity calibration, uncertainty in stellar mass determination, aperture effects, and dust. We present the first analysis of the relation between stellar mass, gas phase metallicity, and SFR using strong line abundance diagnostics from Dopita et al. (2013) for ~130,000 star-forming galaxies in the Sloan Digital Sky Survey and provide a detailed comparison of these diagnostics in an appendix. Using these abundance ...

  4. Treatment of reduced sulphur compounds and SO2 by Gas Phase Advanced Oxidation

    DEFF Research Database (Denmark)

    Meusinger, Carl; Bluhme, Anders Brostrøm; Ingemar, Jonas L.

    2017-01-01

    Reduced sulphur compounds (RSCs) emitted from pig farms are a major problem for agriculture, due to their health and environmental impacts and foul odour. This study investigates the removal of RSCs, including H2S, and their oxidation product SO2 using Gas Phase Advanced Oxidation (GPAO). GPAO is...... compounds. The study demonstrates the ability of GPAO to control RSC emissions with a low energy input relative to many currently available techniques. (C) 2016 Elsevier B.V. All rights reserved......., assuming the observed particles were made of sulphuric acid. In a second set of experiments a range of RSCs at mixing ratios typically found in pig farms were treated using a larger industry-scale system (Q = 600-1200 m3/h) that included a wet scrubber. Removal efficiencies >90% were found for all...

  5. Liquid- and Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Wencai Zhou

    2015-06-01

    Full Text Available The mass transfer of the guest molecules in nanoporous host materials, in particular in metal-organic frameworks (MOFs, is among the crucial features of their applications. By using thin surface-mounted MOF films in combination with a quartz crystal microbalance (QCM, the diffusion of ferrocene vapor and of ethanolic and hexanic ferrocene solution in HKUST-1 was investigated. For the first time, liquid- and gas-phase diffusion in MOFs was compared directly in the identical sample. The diffusion coefficients are in the same order of magnitude (~10−16 m2·s−1, whereas the diffusion coefficient of ferrocene in the empty framework is roughly 3-times smaller than in the MOF which is filled with ethanol or n-hexane.

  6. Liquid- and Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks

    Science.gov (United States)

    Zhou, Wencai; Wöll, Christof; Heinke, Lars

    2015-01-01

    The mass transfer of the guest molecules in nanoporous host materials, in particular in metal-organic frameworks (MOFs), is among the crucial features of their applications. By using thin surface-mounted MOF films in combination with a quartz crystal microbalance (QCM), the diffusion of ferrocene vapor and of ethanolic and hexanic ferrocene solution in HKUST-1 was investigated. For the first time, liquid- and gas-phase diffusion in MOFs was compared directly in the identical sample. The diffusion coefficients are in the same order of magnitude (~10−16 m2·s−1), whereas the diffusion coefficient of ferrocene in the empty framework is roughly 3-times smaller than in the MOF which is filled with ethanol or n-hexane.

  7. UV/Vis Action Spectroscopy and Structures of Tyrosine Peptide Cation Radicals in the Gas Phase.

    Science.gov (United States)

    Viglino, Emilie; Shaffer, Christopher J; Tureček, František

    2016-06-20

    We report the first application of UV/Vis photodissociation action spectroscopy for the structure elucidation of tyrosine peptide cation radicals produced by oxidative intramolecular electron transfer in gas-phase metal complexes. Oxidation of Tyr-Ala-Ala-Ala-Arg (YAAAR) produces Tyr-O radicals by combined electron and proton transfer involving the phenol and carboxyl groups. Oxidation of Ala-Ala-Ala-Tyr-Arg (AAAYR) produces a mixture of cation radicals involving electron abstraction from the Tyr phenol ring and N-terminal amino group in combination with hydrogen-atom transfer from the Cα positions of the peptide backbone. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Accurate Structure Parameters for Tunneling Ionization Rates of Gas-Phase Linear Molecules

    Science.gov (United States)

    Zhao, Song-Feng; Li, Jian-Ke; Wang, Guo-Li; Li, Peng-Cheng; Zhou, Xiao-Xin

    2017-03-01

    In the molecular Ammosov–Delone–Krainov (MO-ADK) model of Tong et al. [Phys. Rev. A 66 (2002) 033402], the ionization rate depends on the structure parameters of the molecular orbital from which the electron is removed. We determine systematically and tabulate accurate structure parameters of the highest occupied molecular orbital (HOMO) for 123 gas-phase linear molecules by solving time-independent Schrödinger equation with B-spline functions and molecular potentials which are constructed numerically using the modified Leeuwen–Baerends (LBα) model. Supported by National Natural Science Foundation of China under Grant Nos. 11664035, 11674268, 11465016, 11364038, 11364039, the Specialized Research Fund for the Doctoral Program of Higher Education of China under Grant No. 20116203120001 and the Basic Scientific Research Foundation for Institution of Higher Learning of Gansu Province

  9. Thermodynamic and kinetic stability of zwitterionic histidine: Effects of gas phase hydration

    Science.gov (United States)

    Lee, Sung-Sik; Kim, Ju-Young; Han, Yuna; Shim, Hyun-Jin; Lee, Sungyul

    2015-09-01

    We present calculations for histidine-(H2O)n (n = 0-6) to examine the effects of micro-hydrating water molecules on the relative stability of the zwitterionic vs. canonical forms of histidine. We calculate the structures and Gibbs free energies of the conformers at wB97XD/6-311++G(d,p) level of theory. We find that six water molecules are required to produce the thermodynamically stable histidine zwitterion. By calculating the barriers of canonical ↔ zwitterionic transformation, we predict that both the most stable canonical and zwitterionic forms of histidine-(H2O)6 may be observed in low temperature gas phase environment.

  10. Stability of polyphenols in chokeberry juice treated with gas phase plasma.

    Science.gov (United States)

    Bursać Kovačević, Danijela; Gajdoš Kljusurić, Jasenka; Putnik, Predrag; Vukušić, Tomislava; Herceg, Zoran; Dragović-Uzelac, Verica

    2016-12-01

    Chokeberry juice was subjected to cold atmospheric gas phase plasma and changes in hydroxycinnamic acids, flavonols and anthocyanins were monitored. Plasma treatments were carried out under different treatment times and juice volumes under constant gas flow (0.75dm(3)min(-1)). The results were compared against control (untreated) and pasteurized chokeberry juice (80°C/2min). During pasteurization, the most unstable were hydroxycinnamic acids with losses of up to 59%, while flavonols and anthocyanins increased by 5% and 9%, respectively. On the contrary, plasma treated chokeberry juice showed higher concentrations of hydroxycinnamic acids and 23% loss of anthocyanins in comparison to untreated juice. In order to obtain the optimal cold plasma treatment parameters principal component and sensitivity analysis were used. Such parameters can be potentially used for pasteurization in terms of phenolic stability of chokeberry juice. Optimal treatment was at 4.1min and sample volume of 3cm(3). Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. DFT study of the reactions of Mo and Mo+ with CO2 in gas phase

    Indian Academy of Sciences (India)

    Deman Han; Guoliang Dai; Hao Chen; Hua Yan; Junyong Wu; Chuanfeng Wang; Aiguo Zhong

    2011-05-01

    Density functional theory (DFT) calculations have been performed to explore the potential energy surfaces of C-O bond activation in CO2 molecule by gas-phase Mo+ cation and Mo atom, in order to better understanding the mechanism of second-row metal reacting with CO2. The minimum energy reaction path is found to involve the spin inversion in the different reaction steps. This potential energy curve-crossing dramatically affects reaction exothermic. The present results show that the reaction mechanism is insertion-elimination mechanism along the C-O bond activation branch. All the theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.

  12. Direct gas-phase synthesis of single-phase {beta}-FeSi{sub 2} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Bywalez, Robert, E-mail: robert.bywalez@uni-due.de; Orthner, Hans; Mehmedovic, Ervin [University of Duisburg-Essen, IVG, Institute for Combustion and Gas Dynamics - Reactive Fluids (Germany); Imlau, Robert; Kovacs, Andras; Luysberg, Martina [Forschungszentrum Juelich, Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons and Peter Gruenberg Institute 5 (Germany); Wiggers, Hartmut [University of Duisburg-Essen, IVG, Institute for Combustion and Gas Dynamics - Reactive Fluids (Germany)

    2013-09-15

    For the first time, phase-pure {beta}-FeSi{sub 2} nanoparticles were successfully produced by gas-phase synthesis. We present a method to fabricate larger quantities of semiconducting {beta}-FeSi{sub 2} nanoparticles, with crystallite sizes between 10 and 30 nm, for solar and thermoelectric applications utilizing a hot-wall reactor. A general outline for the production of those particles by thermal decomposition of silane and iron pentacarbonyl is provided based on kinetic data. The synthesized particles are investigated by X-ray diffraction and transmission electron microscopy, providing evidence that the as-prepared materials are indeed {beta}-FeSi{sub 2}, while revealing morphological characteristics inherent to the nanoparticles created.

  13. A generalized expression for lag-time in the gas-phase permeation of hollow tubes

    Science.gov (United States)

    Shah, K. K.; Nelson, H. G.; Johnson, D. L.; Hamaker, F. M.

    1975-01-01

    A generalized expression for the nonsteady-state parameter, lag-time, has been obtained from Fick's second law for gas-phase transport through hollow, cylindrical membranes. This generalized expression is simplified for three limiting cases of practical interest: (1) diffusion controlled transport, (2) phase boundary reaction control at the inlet surface, and (3) phase boundary reaction control at the outlet surface. In all three cases the lag-time expressions were found to be inversely proportional only to the diffusion coefficient and functionally dependent on the membrane radii. Finally, the lag-time expressions were applied to experimentally obtained lag-time data for alpha-phase titanium and alpha-phase iron.

  14. Nonlinear two-dimensional terahertz photon echo and rotational spectroscopy in the gas phase

    CERN Document Server

    Lu, Jian; Hwang, Harold Y; Ofori-Okai, Benjamin K; Fleischer, Sharly; Nelson, Keith A

    2016-01-01

    Ultrafast two-dimensional spectroscopy utilizes correlated multiple light-matter interactions for retrieving dynamic features that may otherwise be hidden under the linear spectrum. Its extension to the terahertz regime of the electromagnetic spectrum, where a rich variety of material degrees of freedom reside, remains an experimental challenge. Here we report ultrafast two-dimensional terahertz spectroscopy of gas-phase molecular rotors at room temperature. Using time-delayed terahertz pulse pairs, we observe photon echoes and other nonlinear signals resulting from molecular dipole orientation induced by three terahertz field-dipole interactions. The nonlinear time-domain orientation signals are mapped into the frequency domain in two-dimensional rotational spectra which reveal J-state-resolved nonlinear rotational dynamics. The approach enables direct observation of correlated rotational transitions and may reveal rotational coupling and relaxation pathways in the ground electronic and vibrational state.

  15. Gas-Phase Interactions as Sources of Contamination in Solar Silicon

    Science.gov (United States)

    Meteleva-Fischer, Y. V.; Böttger, A. J.; Sloof, W. G.; Kraaijveld, B.

    2014-06-01

    Avoiding contamination of silicon for solar cells during high-temperature processing steps is a key issue. Contamination of silicon via direct contact due to diffusion processes has been recognized. Here, it is shown that interactions with the gas phase also are a potential source of contamination. Thermodynamic calculations performed for a temperature range of 373 K to 1873 K (100 °C to 1600 °C) and total pressure of 10 kPa predict the formation of volatile species that are harmful for photovoltaic properties. Volatile species form due to graphite-moisture interaction and the interaction of this gas mixture with compounds commonly present in silicon production units: graphite, quartz, alumina, boron nitride, and iron. The results of the calculations are supported by the data of the surface contamination of exposed graphite furnace parts.

  16. Non-congruence of liquid-gas phase transition of asymmetric nuclear matter

    CERN Document Server

    Maruyama, Toshiki

    2012-01-01

    We first explore the liquid-gas mixed phase in a bulk calculation, where two phases coexist without the geometrical structures. In the case of symmetric nuclear matter, the system behaves congruently, and the Maxwell construction becomes relevant. For asymmetric nuclear matter, on the other hand, the phase equilibrium is no more attained by the Maxwell construction since the liquid and gas phases are non-congruent; the particle fractions become completely different with each other. One of the origins of such non-congruence is attributed to the large symmetry energy. Subsequently we explore the charge-neutral nuclear matter with electrons by fully applying the Gibbs conditions to figure out the geometrical (pasta) structures in the liquid-gas mixed phase. We emphasize the effects of the surface tension and the Coulomb interaction on the pasta structures. We also discuss the thermal effects on the pasta structures.

  17. Theoretical Investigation of Tautomerism Stability of Hydantoin in the Gas Phase and in the Solution

    Directory of Open Access Journals (Sweden)

    Wala W. Fares

    2014-09-01

    Full Text Available The relative stability of the different tautomers of hydantoin has been studied through the use of DFT method. The structures and the vibrational frequencies of all stable tautomers and all the transitions states connecting between them have been calculated at the B3LYP/6-311+G(d,p level of theory in the gas phase and selected solvents using IE-PCM model. Final energies have been obtained in single-point B3LYP/6-311++(3df,2p calculations. The results show that the diketo tautomer T1 is more stable than the other tautomers. Variation of charge densities at bond critical points, dipole moments and NBO charges on atoms in the solvents were studied.

  18. New studies on molecular chirality in the gas phase: enantiomer differentiation and determination of enantiomeric excess.

    Science.gov (United States)

    Patterson, David; Schnell, Melanie

    2014-06-21

    Chirality plays a fundamental role in the activity of biological molecules and broad classes of chemical reactions. The chemistry of life is built almost exclusively on left-handed amino acids and right-handed sugars, a phenomenon known as "homochirality of life". Furthermore, most drugs developed in the last decade are of specified chirality. Thus, fast and reliable methods that can differentiate molecules of different handedness, determine the enantiomeric excess of even molecular mixtures, and allow for an unambiguous determination of molecular handedness are of great interest, in particular with respect to complex mixtures. In this perspective article, we discuss the recent developments, with an emphasis on modern spectroscopic methods using gas-phase samples, such as photoelectron circular dichroism, Coulomb explosion imaging, and microwave three-wave mixing.

  19. How does deposition of gas phase species affect pH at frozen salty interfaces?

    Directory of Open Access Journals (Sweden)

    S. N. Wren

    2012-08-01

    Full Text Available Chemical processes occurring on snow and ice surfaces play an important role in controlling the oxidative capacity of the overlying atmosphere. However, efforts to gain a better, mechanistic understanding of such processes are impeded by our poor understanding of the chemical nature of the air-ice interface. Here we use a surface-sensitive spectroscopic technique to investigate how the nature of the ice, whether frozen freshwater, salt water or seawater, influences pH changes at the surface. Deposition of HCl(g leads to a very different pH response at the frozen freshwater surface than at the frozen salt water surface indicating that these two surfaces present different chemical environments. Importantly, the sea ice surface is buffered against pH changes arising from deposition of gas phase species. These results have important implications for understanding pH-sensitive processes occurring at the air-ice boundary, such as bromine activation.

  20. An improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions

    CERN Document Server

    Kraft, M

    2003-01-01

    We propose an improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions. By combining forward and reverse reaction rates, a significant gain in computational efficiency is achieved. Two modifications of modelling the temperature dependence (with and without conservation of enthalpy) are introduced and studied quantitatively. The algorithm is tested for the combustion of n-heptane, which is a reference fuel component for internal combustion engines. The convergence of the algorithm is studied by a series of numerical experiments and the computational cost of the stochastic algorithm is compared with the DAE code DASSL. If less accuracy is needed the stochastic algorithm is faster on short simulation time intervals. The new stochastic algorithm is significantly faster than the original direct simulation algorithm in all cases considered.

  1. Photodissociation and spectroscopy of gas phase bimetallic clusters. Progress report for 1990--1991

    Energy Technology Data Exchange (ETDEWEB)

    Duncan, M.A.

    1991-12-31

    The general goals of this research project are (1) to synthesize novel bimetallic clusters in the gas phase; (2) to characterize their geometry, electronic structure, and chemical bonding; and (3) to compare these heterogeneous systems to corresponding pure component clusters. Clusters are synthesized by pulsed laser vaporization of solid metal rods coincident with laser photolysis of volatile metal complexes (e.g., metal carbonyls). Two techniques are used to characterize cluster properties: resonant two-photon ionization spectroscopy (R2PI) of neutral clusters and laser photodissociation spectroscopy of cluster ions. The project focuses on the selected mixtures of iron, chromium, and molybdenum with bismuth, aluminum and silver to probe a variety of heterogeneous effects in transition metal-main group metal mixtures.

  2. Identification of the dimethylamine-trimethylamine complex in the gas phase.

    Science.gov (United States)

    Du, Lin; Lane, Joseph R; Kjaergaard, Henrik G

    2012-05-14

    We have identified the dimethylamine-trimethylamine complex (DMA-TMA) at room temperature in the gas phase. The Fourier transform infrared (FTIR) spectrum of DMA-TMA in the NH-stretching fundamental region was obtained by spectral subtraction of spectra of each monomer. Explicitly correlated coupled cluster calculations were used to determine the minimum energy structure and interaction energy of DMA-TMA. Frequencies and intensities of NH-stretching transitions were also calculated at this level of theory with an anharmonic oscillator local mode model. The fundamental NH-stretching intensity in DMA-TMA is calculated to be approximately 700 times larger than that of the DMA monomer. The measured and calculated intensity is used to determine a room temperature equilibrium constant of DMA-TMA of 1.7 × 10(-3) atm(-1) at 298 K.

  3. A detailed investigation of proposed gas-phase syntheses of ammonia in dense interstellar clouds

    Science.gov (United States)

    Herbst, Eric; Defrees, D. J.; Mclean, A. D.

    1987-01-01

    The initial reactions of the Herbst and Klemperer (1973) and the Dalgarno (1974) schemes (I and II, respectively) for the gas-phase synthesis of ammonia in dense interstellar clouds were investigated. The rate of the slightly endothermic reaction between N(+) and H2 to yield NH(+) and H (scheme I) under interstellar conditions was reinvestigated under thermal and nonthermal conditions based on laboratory data. It was found that the relative importance of this reaction in synthesizing ammonia is determined by how the laboratory data at low temperature are interpreted. On the other hand, the exothermic reaction between N and H3(+) to form NH2(+) + H (scheme II) was calculated to possess significant activation energy and, therefore, to have a negligible rate coefficient under interstellar conditions. Consequently, this reaction cannot take place appreciably in interstellar clouds.

  4. Gas-Phase Beckmann Rearrangement of Cyclohexanone Oxime over B-ZSM-5 Derived Titanosilicalite

    Institute of Scientific and Technical Information of China (English)

    尹双凤; 张法智; 徐柏庆

    2002-01-01

    Four different ZSM-5 zeolites are tested for the gas-phase Beckmann rearrangement of cyclohexanone oxime (CHO) into lactam. B-ZSM-5 derived titanosilicalite (Ti-ZSM-5) exhibits catalytic performances comparable to hydrothermally synthesized titanosilicalite (TS-1), much better than B-ZSM-5 and Al-ZSM-5. The effect of reaction conditions (solvent, feed space velocity, and water) on the catalytic performance of Ti-ZSM-5 is studied. It is found that a quantitative relationship exists among the feed space velocity, the reaction time, and the CHO constant conversion. Ethanol or methanol as solvent shows higher activity, lactam selectivity, and stability than benzene and n-hexanol. The addition of water to the rearrangement with a maximum amount of 1.0 mole per mole CHO results in the increase of CHO conversion while no meaningful changes in lactam selectivity and stability are observed.

  5. Gas phase reaction of phosphorus trichloride and methanol: Matrix isolation infrared and DFT studies

    Science.gov (United States)

    Joshi, Prasad Ramesh; Ramanathan, N.; Sundararajan, K.; Sankaran, K.

    2015-11-01

    Gas phase reaction of phosphorus trichloride (PCl3) and methanol (CH3OH) was carried out with different ratios of PCl3:CH3OH:N2 (1:1:1000, 1:2:1000 and 1:3:1000) and the products were identified using matrix isolation infrared spectroscopy. For the 1:1 and 1:2 ratios of PCl3:CH3OH, dichloro methyl phosphite (DCMP) and methyl chloride (CH3Cl) were the products formed. Interestingly, only methyl chloride (CH3Cl) was observed for the 1:3 ratio of PCl3:CH3OH. DFT computations were carried out at B3LYP/6-311++G(d,p) level of theory to give insights into the formation of the reaction products. Based on the experimental findings and computations a reaction mechanism has been proposed through a nucleophilic substitution reaction to explain the formation of the products.

  6. Why do high-redshift galaxies show diverse gas-phase metallicity gradients?

    CERN Document Server

    Ma, Xiangcheng; Feldmann, Robert; Torrey, Paul; Faucher-Giguere, Claude-Andre; Keres, Dusan

    2016-01-01

    Recent spatially resolved observations of galaxies at z=0.6-3 reveal that high-redshift galaxies show complex kinematics and a broad distribution of gas-phase metallicity gradients. To understand these results, we use a suite of high-resolution cosmological zoom-in simulations from the Feedback in Realistic Environments (FIRE) project, which include physically motivated models of the multi-phase ISM, star formation, and stellar feedback. Our simulations reproduce the observed diversity of kinematic properties and metallicity gradients, broadly consistent with observations at z=0-3. Strong negative metallicity gradients only appear in galaxies with a rotating disk, but not all rotationally supported galaxies have significant gradients. Strongly perturbed galaxies with little rotation always have flat gradients. The kinematic properties and metallicity gradient of a high-redshift galaxy can vary significantly on short time-scales, associated with starburst episodes. Feedback from a starburst can destroy the gas...

  7. Gas-phase hydration thermochemistry of sodiated and potassiated nucleic acid bases.

    Science.gov (United States)

    Wincel, Henryk

    2012-09-01

    Hydration reactions of sodiated and potassiated nucleic acid bases (uracil, thymine, cytosine, and adenine) produced by electrospray have been studied in a gas phase using the pulsed ion-beam high-pressure mass spectrometer. The thermochemical properties, ΔH(o)(n), ΔS(o)(n), and ΔG(o)(n), for the hydrated systems were obtained from hydration equilibrium measurement. The structural aspects of the hydrated complexes are discussed in conjunction with available literature data. The correlation between water binding energies in the hydrated complexes and the corresponding metal ion affinities of nucleobases suggests that a significant (if not dominant) amount of the canonical structure of cytosine undergoes tautomerization during electrospray ionization, and the thermochemical values for cationized cytosine probably correspond to a mixture of tautomeric complexes.

  8. Treatment of reduced sulphur compounds and SO2 by Gas Phase Advanced Oxidation

    DEFF Research Database (Denmark)

    Meusinger, Carl; Bluhme, Anders Brostrøm; Ingemar, Jonas L.

    2017-01-01

    Reduced sulphur compounds (RSCs) emitted from pig farms are a major problem for agriculture, due to their health and environmental impacts and foul odour. This study investigates the removal of RSCs, including H2S, and their oxidation product SO2 using Gas Phase Advanced Oxidation (GPAO). GPAO...... is a novel air cleaning technique which utilises accelerated atmospheric chemistry to oxidise pollutants before removing their oxidation products as particles. Removal efficiencies of 24.5% and 3.9% were found for 461 ppb of H2S and 714 ppb of SO2 in a laboratory system (volumetric flow Q = 75 m3/h...... compounds. The study demonstrates the ability of GPAO to control RSC emissions with a low energy input relative to many currently available techniques. (C) 2016 Elsevier B.V. All rights reserved....

  9. Direct Method Gas Phase Oxygen Abundances of 4 Lyman Break Analogs

    CERN Document Server

    Brown, Jonathan S; Pogge, Richard W

    2014-01-01

    We measure the gas-phase oxygen abundances in 4 Lyman Break Analogs (LBAs) using auroral emission lines to derive direct abundances. The direct method oxygen abundances of these objects are generally consistent with the empirically-derived strong-line method values, confirming that these objects are low oxygen abundance outliers from the Mass-Metallicity (MZ) relation defined by star forming SDSS galaxies. We find slightly anomalous excitation conditions (Wolf-Rayet features) that could potentially bias the empirical estimates towards high values if caution is not exercised in the selection of the strong-line calibration used. The high rate of star formation and low oxygen abundance of these objects is consistent with the predictions of the Fundamental Metallicity Relation (FMR), in which the infall of relatively unenriched gas simultaneously triggers an episode of star formation and dilutes ISM of the host galaxy.

  10. Photo-fragmentation and electron-detachment studies of gas-phase chromophore ions

    DEFF Research Database (Denmark)

    Rahbek, Dennis Bo

    -physical properties of two important bio-chromophores by investigating the properties of structural isomers of these molecules. The chromophores are the ones found in the green fluorescent protein and the photoactive yellow protein. The photo-physical properties have been studied experimentally in the gas phase...... excitation energy. This results in a competition between de-excitation by internal conversion and electron emission. Both of these processes are of non-adiabatic character as they rely on coupling between electronic energy and energy in nuclear motion. Moreover, it is found that higher-lying states...... in the anionic forms serves as ‘doorway’- states into the continuum of the neutral radical. Regarding the structural isomeric forms of each of the chromophores we find that the degree of electronic coupling between the subunitsmaking up the chromophores is crucial for the tuning the absorption properties, both...

  11. Multifragmentation and the liquid-gas phase transition: an experimental overview

    CERN Document Server

    Trautmann, W

    2005-01-01

    Two roads are presently being followed in order to establish the existence of a liquid-gas phase transition in finite nuclear systems from nuclear reactions at high energy. The clean experiment of observing the thermodynamic properties of a finite number of nucleons in a container is presently only possible with the computer. Performed with advanced nuclear transport models, it has revealed the first-order character of the transition and allowed the extraction of the pertinent thermodynamic parameters. The validity of the applied theory is being confirmed by comparing its predictions for heavy-ion reactions with exclusive experiments. The second approach is experimentally more direct. Signals of the transition are searched for by analysing reaction data within the framework of thermodynamics of small systems. A variety of potential signals has been investigated and found to be qualitatively consistent with the expectations for the phase transition. Many of them are well reproduced with percolation models whic...

  12. Detailed kinetics of methylphenyldichlorosilane synthesis from methyldichlorosilane and chlorobenzene by gas phase condensation

    Institute of Scientific and Technical Information of China (English)

    Tong Liu; Tiefeng Wang; Yunlong Huang; Chao Wang; Jinfu Wang

    2015-01-01

    Methylphenyldichlorosilane (MPDS, CH3C6H5SiCl2) is an important silicone monomer for the synthesis of high-performance polymethylphenylsiloxane polymers. In this work, the mechanism of the synthesis of MPDS from methyldichlorosilane and chlorobenzene by gas phase condensation was studied, and a kinetic model with 35 species and 58 elementary reactions was established. Experiments were carried out in a tubular reactor under a wide range of reaction conditions. The calculated mole fractions of the reactants and products were in a good agreement with the experimental results. A mechanism of the insertion of chloromethylsilylene into the C-Cl bond of chlorobenzene was proposed, which was proved to be the main pathway of MPDS production. The established kinetic model can be used in design and optimization of the industrial reactor for MPDS synthesis.

  13. Diffuse Interstellar Bands: How Are They Related to Known Gas-Phase Constituents of the ISM?

    CERN Document Server

    Welty, Daniel E

    2013-01-01

    In this brief review of recent work relating the DIBs to other gas-phase constituents of the ISM, we explore correlations between DIB equivalent widths and the column densities of various atomic and molecular species, drawn from a large database constructed for that purpose. The tightness and slopes of the correlations can provide information on how the DIBs might be related to those species (physically, chemically, spatially) and on various properties of the DIB carriers. Deviations from the mean relationships can reveal dependences of DIB strengths on other parameters, regional variations in DIB behavior, and individual sight lines where unusual environmental conditions affect the DIBs. Variations in DIB profiles (e.g., wings, substructure) and relative strengths may be related to differences in physical conditions inferred from atomic and/or molecular absorption lines.

  14. Simulation of gas phase reactions for microcrystalline silicon films fabricated by PECVD

    Institute of Scientific and Technical Information of China (English)

    HE Bao-hua; YANG Shi-e; CHEN Yong-sheng; LU Jing-xiao

    2011-01-01

    We present a numerical gas phase reaction model for hydrogenated microcrystaUine silicon (μc-Si:H) films fi'om SiH and H gas mixtures with plasma enhanced chemical vapor deposition (PECVD). Under the typical μc-Si:H deposition conditions, the concentrations of the species in the plasma are calculated and the effects of silane fraction (SF=[SiH]/[H+SiH]) are investigated. The results show that SiH is the key precursor for μc-Si:H films growth, and other neutral radicals, such as SiH, SiH and SiH, may play some roles in the film deposition. With the silane fraction increasing, the precursor concentration increases, but H atom concentration decreases rapidly, which results in the lower H/SiH ratio.

  15. STM and HREELS investigation of gas phase silanization on hydroxylated Si(100)

    Science.gov (United States)

    Fan, C.; Lopinski, G. P.

    2010-06-01

    The gas phase anhydrous reaction of glycidoxypropyldimethylethoxysilane (GPDMES) with a model hydroxylated surface has been investigated using high-resolution electron energy loss spectroscopy (HREELS) and scanning tunneling microscopy (STM). Water dissociation on the clean reconstructed (2 × 1)-Si(100) surface was used to create an atomically flat surface with ~ 0.5 ML of hydroxyl groups. Exposure of this surface to GPDMES at room temperature under vacuum was found to lead to formation of covalent Si-O-Si bonds although high exposures (6 × 10 8 L) were required for saturation. STM images at the early stages of reaction indicate that the reaction occurs randomly on the surface with no apparent clustering. The STM images together with semi-empirical (AM1) calculations provide evidence for hydrogen bonding interactions between the oxygen atoms in the molecule and surface hydroxyl groups at low coverage.

  16. Structural Isomerization of the Gas Phase 2-NORBORNYL Cation Revealed with Infrared Spectroscopy and Computational Chemistry

    Science.gov (United States)

    Mauney, Daniel; Mosley, Jonathan; Duncan, Michael A.

    2014-06-01

    The non-classical structure of the 2-norborny cation (C_7H11+) which was at the center of "the most heated chemical controversy of our time" has been observed in the condensed phase and recently using X-ray crystallography. However, no gas phase vibrational spectrum has been collected. The C_7H11+ cation is produced via H_3+ protonation of norbornene by pulsed discharge in a supersonic expansion of H_2/Ar. Ions are mass-selected and probed using infrared photodissociation spectroscopy. Due to high exothermicity, protonation via H_3+ leads to a structural isomerization to the global minimum structure 1,3-dimethylcyclopentenyl (DMCP+). Experiments are currently being conducted to find softer protonation techniques that could lead to the authentic 2-norbornyl cation. Schleyer,P.v.R. et. al.; Stable Carbocation Chemistry, John Wiley & Sons,Inc.; New York, 1997, Chapter 2

  17. Modeling of gas phase diffusion transport during chemical vapor infiltration process

    Institute of Scientific and Technical Information of China (English)

    肖鹏; 李娣; 徐永东; 黄伯云

    2002-01-01

    In order to improve the uniformity of both the concentration of gaseous reagent and the deposition of matrix within micro-pores during the chemical vapor infiltration (CVI) process, a calculation modeling of gas phase diffusion transport within micro-pores was established. Taken CH3SiCl3 as precursor for depositing SiC as example, the diffusion coefficient, decomposing reaction rate, concentration within the reactor, and concentration distributing profiling of MTS within micro-pore were accounted, respectively. The results indicate that, increasing the ratio of diffusion coefficient to decomposition rate constant of precursor MTS is propitious to decrease the densification gradient of parts, and decreasing the aspect ratio (L/D) of micro-pore is favorable to make the concentration uniform within pores.

  18. Gas phase synthesis of core-shell Fe@FeO x magnetic nanoparticles into fluids

    Science.gov (United States)

    Aktas, Sitki; Thornton, Stuart C.; Binns, Chris; Denby, Phil

    2016-12-01

    Sorbitol, short chain molecules, have been used to stabilise of Fe@FeO x nanoparticles produced in the gas phase under the ultra-high vacuum (UHV) conditions. The sorbitol coated Fe@FeO x nanoparticles produced by our method have a narrow size distribution with a hydrodynamic diameter of 35 nm after NaOH is added to the solution. Magnetisation measurement shows that the magnetic nanoparticles are superparamagnetic at 100 K and demonstrate hysteresis at 5 K with an anisotropy constant of 5.31 × 104 J/m3 (similar to bulk iron). Also, it is shown that sorbitol is only suitable for stabilising the Fe@FeO x suspensions, and it does not prevent further oxidation of the metallic Fe core. According to MRI measurement, the nanoparticles have a high transverse relaxation rate of 425 mM-1 s-1.

  19. Iron-carbon nanocomposite obtained by laser-induced gas-phase reactions

    Science.gov (United States)

    Dumitrache, Florian V.; Morjan, Ion G.; Alexandrescu, Rodica; Rand, B.; Ciupina, Victor; Prodan, G.; Voicu, Ion N.; Sandu, Ioan C.; Soare, I.; Ploscaru, M.; Fleaca, C.; Brydson, R.; Vasile, Eugen

    2003-07-01

    Iron-carbon composite nanopowders have been synthesized by the CO2 laser pyrolysis of gas-phase reactants. The experimental device allows for a very low reaction time and a rapid freezing that creates nanoscale-condensed particles. Iron pentacarbonyl and ethylene-acetylene mixtures were used as iron and carbon precursors. In a two-steps experiment, the reaction products may present themselves as iron-based nanoparticles dispersed in a carbon matrix. By a careful control of experimental parameters and radiation geometries we demonstrate the feasibility of an efficient and well-controlled, single-step technique for the production of iron-based nano-cores embedded in carbon layers. Highly dispersed nanoparticles, narrow size distributions and particles with about 4.5 - 6 nm mean diameters were obtained. Electron microscopy and Raman spectroscopy were used in order to analyze the structure and composition of the obtained nanopowders as well as their Soxhlet residue.

  20. Gas-Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN.

    Science.gov (United States)

    Wu, Zhuang; Li, Dingqing; Li, Hongmin; Zhu, Bifeng; Sun, Hailong; Francisco, Joseph S; Zeng, Xiaoqing

    2016-01-22

    The dipolar oxathiazyne-like sulfinylnitrene RS(O)N, a highly reactive α-oxo nitrene, has been rarely investigated. Upon flash vacuum pyrolysis of sulfinyl azide CF3S(O)N3 at 350 °C, an elusive sulfinylnitrene CF3S(O)N was generated in the gas phase in its singlet ground state and was characterized by matrix-isolation IR spectroscopy. Further fragmentation of CF3S(O)N at 600 °C produced CF3 and a novel iminyl radical OSN, an SO2 analogue, which were unambiguously identified by IR spectroscopy. Consistent with the experimental observations, DFT calculations clearly support a stepwise decomposition mechanism of CF3S(O)N3. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Carbonyl Diisocyanate CO(NCO)2: Synthesis and Structures in Solid State and Gas Phase.

    Science.gov (United States)

    Klapötke, Thomas M; Krumm, Burkhard; Rest, Sebastian; Scharf, Regina; Schwabedissen, Jan; Stammler, Hans-Georg; Mitzel, Norbert W

    2016-07-01

    A modified synthesis for carbonyl diisocyanate, CO(NCO)2, starting from trichloroisocyanuric acid and diphosgene is described. In addition to the previously reported (13)C NMR resonances, the (15)N NMR shift is determined for the first time. The structure in the solid state was determined by X-ray diffraction (XRD) on in situ grown crystals, that in the gas phase was experimentally determined by electron diffraction (GED) and for single molecules theoretically by quantum-chemical calculations. The structures are compared and discussed with related systems. Quantum-chemical calculations as well as GED and XRD prove syn-syn to be the conformation of lowest energy. In quantum-chemical calculations and GED the presence of a syn-anti conformer was confirmed and the structure of this conformer was determined.

  2. Formation of PAHs and Carbonaceous Solids in Gas-Phase Condensation Experiments

    CERN Document Server

    Jäger, C; Jansa, I Llamas; Henning, T; Huisken, F

    2009-01-01

    Carbonaceous grains represent a major component of cosmic dust. In order to understand their formation pathways, they have been prepared in the laboratory by gas-phase condensation reactions such as laser pyrolysis and laser ablation. Our studies demonstrate that the temperature in the condensation zone determines the formation pathway of carbonaceous particles. At temperatures lower than 1700 K, the condensation by-products are mainly polycyclic aromatic hydrocarbons (PAHs), that are also the precursors or building blocks for the condensing soot grains. The low-temperature condensates contain PAH mixtures that are mainly composed of volatile 3-5 ring systems. At condensation temperatures higher than 3500 K, fullerene-like carbon grains and fullerene compounds are formed. Fullerene fragments or complete fullerenes equip the nucleating particles. Fullerenes can be identified as soluble components. Consequently, condensation products in cool and hot astrophysical environments such as cool and hot AGB stars or W...

  3. Electronic Wave Packet Interferometry of Gas Phase Samples: High Resolution Spectra and Collective Effects

    Science.gov (United States)

    Stienkemeier, Frank

    2017-06-01

    Time-resolved coherent spectroscopy has opened many new directions to study ultrafast dynamics in complex quantum systems. While most applications have been achieved in the condensed phase, we are focusing on dilute gas phase samples, in particular, on doped helium droplet beams. Isolation in such droplets at millikelvin temperatures provides unique opportunities to synthesize well-defined complexes, to prepare specific ro-vibronic states, and study their dynamics. To account for the small densities in our samples, we apply a phase modulation technique in order to reach enough sensitivity and a high spectral resolution in electronic wave packet interferometry experiments. The combination with mass-resolved ion detection enabled us e.g. to characterize vibrational structures of excimer molecules. By extending this technique we have observed collective resonances in samples of very low density (10^8 cm^{-3}). With a variant of this method, we are currently elaborating the implementation of nonlinear all-XUV spectroscopy.

  4. Relaxation rates of low-field gas-phase ^129Xe storage cells

    Science.gov (United States)

    Limes, Mark; Saam, Brian

    2010-10-01

    A study of longitudinal nuclear relaxation rates T1 of ^129Xe and Xe-N2 mixtures in a magnetic field of 3.8 mT is presented. In this regime, intrinsic spin relaxation is dominated by the intramolecular spin-rotation interaction due to persistent xenon dimers, a mechanism that can be quelled by introducing large amounts of N2 into the storage cell. Extrinsic spin relaxation is dominated by the wall-relaxation rate, which is the primary quantity of interest for the various low-field storage cells and coatings that we have tested. Previous group work has shown that extremely long gas-phase relaxation times T1 can be obtained, but only at large magnetic fields and low xenon densities. The current work is motivated by the practical benefits of retaining hyperpolarized ^129Xe for extended periods of time in a small magnetic field.

  5. Electrons Mediate the Gas-Phase Oxidation of Formic Acid with Ozone.

    Science.gov (United States)

    van der Linde, Christian; Tang, Wai-Kit; Siu, Chi-Kit; Beyer, Martin K

    2016-08-26

    Gas-phase reactions of CO3 (.-) with formic acid are studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Signal loss indicates the release of a free electron, with the formation of neutral reaction products. This is corroborated by adding traces of SF6 to the reaction gas, which scavenges 38 % of the electrons. Quantum chemical calculations of the reaction potential energy surface provide a reaction path for the formation of neutral carbon dioxide and water as the thermochemically favored products. From the literature, it is known that free electrons in the troposphere attach to O2 , which in turn transfer the electron to O3 . O3 (.-) reacts with CO2 to form CO3 (.-) . The reaction reported here formally closes the catalytic cycle for the oxidation of formic acid with ozone, catalyzed by free electrons.

  6. Gas phase tricholoethylene removal at low concentration using activated carbon fiber

    Institute of Scientific and Technical Information of China (English)

    LIU Jun; HUANG Zheng-hong; WANG Zhan-sheng; KANG Fei-yu

    2004-01-01

    The breakthrough adsorption behaviors of gas phase trichloroethylene in a packed bed of activated carbon fibers(ACF) were investigated. The specific surface area of the ACF was 600 m2/g, 1400 m2/g and 1600 m2/g, respectively, and the concentration of trichioroethylene ranged from 270 mg/m3 to 2700 mg/m3 . Results showed that the capacity of adsorption increased with increasing specific surface area, the relationship between the logarithms of 10% breakthrough time and concentration was approximately linear over the experimental range, the breakthrough time decreased with increasing temperature and humidity. The breakthrough curves at different inlet concentration or different temperature can be predicted by several simple theoretical models with good agreements.

  7. Diffuse Interstellar Bands: How are they related to known Gas-Phase Constituents of the ISM?

    Science.gov (United States)

    Welty, D. E.

    2014-02-01

    In this brief review of recent work relating the DIBs to other gas-phase constituents of the ISM, we explore correlations between DIB equivalent widths and the column densities of various atomic and molecular species, drawn from a large database constructed for that purpose. The tightness and slopes of the correlations can provide information on how the DIBs might be related to those species (physically, chemically, spatially) and on various properties of the DIB carriers. Deviations from the mean relationships can reveal dependences of DIB strengths on other parameters, regional variations in DIB behavior, and individual sight lines where unusual environmental conditions affect the DIBs. Variations in DIB profiles (e.g., wings, substructure) and relative strengths may be related to differences in physical conditions inferred from atomic and/or molecular absorption lines.

  8. Synthesis 1, 3-bis (4-bromophenyl-5-isopropyl-1, 3, 5-triazacyclohexane

    Directory of Open Access Journals (Sweden)

    L. LEFRADA

    2015-03-01

    Full Text Available Condensation of an isopropylamine and an 4-bromoaniline with formaline in basic solution to give 1, 3-bis (4-bromophenyl-5- (isopropyl- 1, 3, 5- triazicyaclohexane. Through the interaction of rapid Schiff base, Structures of this compound have been elucidated by spectroscopic methods; IR, 1H NMR, 13C NMR. Their purities were confirmed by elemental analyses.

  9. 异丙醚提纯工艺的研究%Research Isopropyl Ether Purification Process

    Institute of Scientific and Technical Information of China (English)

    姜丽敏; 位淑华; 张梦博

    2014-01-01

    研究了异丙醚的提纯工艺。采用酸洗的方法,用硫酸做酸化剂与异丙醇副产叠合油中的异丙醚反应,静止分离,水解,精馏得到高纯度的异丙醚。讨论了硫酸质量分数、硫酸与异丙醚的质量比、反应时间对反应的影响,所得异丙醚的质量分数大于99%。%Purification process of isopropyl ether was studied.Sulfuric acid as acidifying reagent reac-ted with isopropyl ether in composite oil which was a byproduct of isopropanol,after still separation,hydroly-sis,distillation,isopropyl ether with high purity was obtained.The content of sulfuric acid,the mass ratio of sulfuric acid to isopropyl ether,the reaction time were discussed,the obtained content of diisopropyl ether was greater than 99%.

  10. THEORETICAL STUDY ON CORROSION INHIBITION PROPERTIES OF 2-ISOPROPYL-5-METHYLPHENOL

    Directory of Open Access Journals (Sweden)

    Saprizal Hadisaputra

    2016-08-01

    Full Text Available Corrosion inhibitors of 2-isopropyl-5-methylphenol and its derivatives has been elucidated by means of density functional theory at B3LYP/6-31G(d level of theory. Effect of electron donating and withdrawing groups such as NH2, SH, CHCH2, CH3, OH, CHO, COOH, F and NO2 on the corrosion inhibitor of 2-isopropyl-5-methylphenol derivatives also have been studied. The quantum chemical parameters such as the frontier orbital energies (EHOMO, ionization potential (I, electron affinity (A and electronegativity (χ are closely related to the corrosion inhibition efficiency (IE % of 2-isopropyl-5-methylphenol derivatives. The presence of electron donating groups increase IE % values meanwhile electron with drawing groups reduce IE % values. The enhancement of IE % follows NO2 < CHO < COOH < SH < F < CH3 < CHCH2 < OH < NH2. Electron donating NH2 group gives 96.38 % of IE %, pure 2-isopropyl-5-methylphenol IE % = 82.70 %. In contrast, electron withdrawing NO2 group gives IE % only 68.66 %. This theoretical study would have a significantly contribution for accelerating corrosion inhibitor experimental to gain optimum results.

  11. A preliminary study of isopropyl alcohol matrix effect and correction in ICP-MS

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Isopropyl alcohol matrix effect was found to be element specific by using the defined matrix effect factor in ICP-MS, which could not be corrected by using the conventional internal reference method. Unlike the conventional internal reference method, the presented method allows for the analyte to behave differently from the internal reference under the influence of the matrix.

  12. Green synthesis of isopropyl myristate in novel single phase medium Part I: Batch optimization studies

    Directory of Open Access Journals (Sweden)

    Rajeshkumar N. Vadgama

    2015-12-01

    Full Text Available Isopropyl myristate finds many applications in food, cosmetic and pharmaceutical industries as an emollient, thickening agent, or lubricant. Using a homogeneous reaction phase, non-specific lipase derived from Candida antartica, marketed as Novozym 435, was determined to be most suitable for the enzymatic synthesis of isopropyl myristate. The high molar ratio of alcohol to acid creates novel single phase medium which overcomes mass transfer effects and facilitates downstream processing. The effect of various reaction parameters was optimized to obtain a high yield of isopropyl myristate. Effect of temperature, agitation speed, organic solvent, biocatalyst loading and batch operational stability of the enzyme was systematically studied. The conversion of 87.65% was obtained when the molar ratio of isopropyl alcohol to myristic acid (15:1 was used with 4% (w/w catalyst loading and agitation speed of 150 rpm at 60 °C. The enzyme has also shown good batch operational stability under optimized conditions.

  13. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

    2011-07-01

    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

  14. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Jorge, Nelly Lidia [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain); Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Romero, Jorge Marcelo [Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Grand, Andre [INAC, SCIB, Laboratoire ' Lesions des Acides Nucleiques' , UMR CEA-UJF E3, CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble cedex 9 (France); Hernandez-Laguna, Alfonso, E-mail: ahlaguna@ugr.es [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain)

    2012-01-17

    Highlights: Black-Right-Pointing-Pointer Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. Black-Right-Pointing-Pointer Gas chromatography and computational potential energy surfaces were performed. Black-Right-Pointing-Pointer A mechanism in steps looked like the most probable mechanism. Black-Right-Pointing-Pointer A spin-orbit coupling appeared at the singlet and triple diradical open structures. Black-Right-Pointing-Pointer A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 {+-} 0.8 kcal/mol and 5.2 Multiplication-Sign 10{sup 13} s{sup -1}, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G{sup Asterisk-Operator Asterisk-Operator} level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  15. Formation of Small Gas Phase Carbonyls from Heterogeneous Oxidation of Polyunsaturated Fatty Acids (PUFA)

    Science.gov (United States)

    Zhou, S.; Zhao, R.; Lee, A.; Gao, S.; Abbatt, J.

    2011-12-01

    Fatty acids (FAs) are emitted into the atmosphere from gas and diesel powered vehicles, cooking, plants, and marine biota. Field measurements have suggested that FAs, including polyunsaturated fatty acids (PUFA), could make up an important contribution to the organic fraction of atmospheric aerosols. Due to the existence of carbon-carbon double bonds in their molecules, PUFA are believed to be highly reactive towards atmospheric oxidants such as OH and NO3 radicals and ozone, which will contribute to aerosol hygroscopicity and cloud condensation nuclei activity. Previous work from our group has shown that small carbonyls formed from the heterogeneous reaction of linoleic acid (LA) thin films with gas-phase O3. It is known that the formation of small carbonyls in the atmosphere is not only relevant to the atmospheric budget of volatile organic compounds but also to secondary organic aerosol formation. In the present study, using an online proton transfer reaction mass spectrometry (PTR-MS) and off-line gas chromatography-mass spectrometry (GC-MS) we again investigated carbonyl formation from the same reaction system, i.e. the heterogeneous ozonolysis of LA film. In addition to the previously reported carbonyls, malondialdehyde (MDA), a source of reactive oxygen species that is mutagenic, has been identified as a product for the first time. Small dicarbonyls, e.g. glyoxal, are expected to be formed from the further oxidation of MDA. In this presentation, the gas-phase chemistry of MDA with OH radicals using a newly built Teflon chamber in our group will also be presented.

  16. Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

    Science.gov (United States)

    Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

    2016-12-01

    The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

  17. Oxidation of elemental mercury by chlorine: Gas phase, Surface,and Photo-induced reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Nai-Qiang; Liu, Shou-Heng; Chang, Shih-Ger

    2004-10-22

    Accurate oxidation rate constants of mercury gas are needed for determining its dispersion and lifetime in the atmosphere. They would also help in developing a technology for the control of mercury emissions from coal-fired power plants. However, it is difficult to establish the accurate rate constants primarily due to the fact that mercury easily adsorbs on solid surface and its reactions can be catalyzed by the surface. We have demonstrated a procedure that allows the determination of gas phase, surface-induced, and photo-induced contributions in the kinetic study of the oxidation of mercury by chlorine gas. The kinetics was studied using reactors with various surface to volume ratios. The effect of the surface and the photo irradiation on the reaction was taken into consideration. The pressure dependent study revealed that the gas phase oxidation was a three-body collision process. The third order rate constant was determined to be 7.5({+-}0.2) x 10{sup -39} mL{sup 2} molecules{sup -2}s{sup -1} with N{sub 2} as the third body at 297 {+-} 1 K. The surface induced reaction on quartz window was second order and the rate constant was 2.7 x 10{sup -17} mL{sup 2} molecules{sup -1} cm{sup -2} sec. Meanwhile, the 253.7 nm photon employed for mercury detection was found to accelerate the reaction. The utilization efficiency of 253.7 nm photon for Hg{sup 0} oxidation was 6.7 x 10{sup -4} molecules photon{sup -1} under the conditions employed in this study.

  18. Description and control of dissociation channels in gas-phase protein complexes

    Science.gov (United States)

    Thachuk, Mark; Fegan, Sarah K.; Raheem, Nigare

    2016-08-01

    Using molecular dynamics simulations of a coarse-grained model of the charged apo-hemoglobin protein complex, this work expands upon our initial report [S. K. Fegan and M. Thachuk, J. Am. Soc. Mass Spectrom. 25, 722-728 (2014)] about control of dissociation channels in the gas phase using specially designed charge tags. Employing a charge hopping algorithm and a range of temperatures, a variety of dissociation channels are found for activated gas-phase protein complexes. At low temperatures, a single monomer unfolds and becomes charge enriched. At higher temperatures, two additional channels open: (i) two monomers unfold and charge enrich and (ii) two monomers compete for unfolding with one eventually dominating and the other reattaching to the complex. At even higher temperatures, other more complex dissociation channels open with three or more monomers competing for unfolding. A model charge tag with five sites is specially designed to either attract or exclude charges. By attaching this tag to the N-terminus of specific monomers, the unfolding of those monomers can be decidedly enhanced or suppressed. In other words, using charge tags to direct the motion of charges in a protein complex provides a mechanism for controlling dissociation. This technique could be used in mass spectrometry experiments to direct forces at specific attachment points in a protein complex, and hence increase the diversity of product channels available for quantitative analysis. In turn, this could provide insight into the function of the protein complex in its native biological environment. From a dynamics perspective, this system provides an interesting example of cooperative behaviour involving motions with differing time scales.

  19. α-Terpineol reactions with the nitrate radical: Rate constant and gas-phase products

    Science.gov (United States)

    Jones, Brian T.; Ham, Jason E.

    The bimolecular rate constant of k rad +α-terpineol (16 ± 4) × 10 -12 cm 3 molecule -1 s -1 was measured using the relative rate technique for the reaction of the nitrate radical (NO 3rad ) with α-terpineol (2-(4-methyl-1-cyclohex-3-enyl)propan-2-ol) at 297 ± 3 K and 1 atmosphere total pressure. To more clearly define part of α-terpineol's indoor environment degradation mechanism, the products of α-terpineol + NO 3rad reaction were investigated. The identified reaction products were: acetone, glyoxal (HC( dbnd O)C( dbnd O)H), and methylglyoxal (CH 3C( dbnd O)C( dbnd O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N, O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose the other major reaction products: 6-hydroxyhept-5-en-2-one, 4-(1-hydroxy-1-methylethyl)-1-methyl-2-oxocyclohexyl nitrate, 5-(1-hydroxy-1-methylethyl)-2-oxocyclohexyl nitrate, 1-formyl-5-hydroxy-4-(hydroxymethyl)-1,5-dimethylhexyl nitrate, and 1,4-diformyl-5-hydroxy-1,5-dimethylhexyl nitrate. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible α-terpineol + NO 3rad reaction mechanisms based on previously published volatile organic compound + NO 3rad gas-phase mechanisms. The additional gas-phase products (2,6,6-trimethyltetrahydro-2 H-pyran-2,5-dicarbaldehyde and 2,2-dimethylcyclohexane-1,4-dicarbaldehyde) are proposed to be the result of cyclization through a reaction intermediate.

  20. Photocatalytic degradation of 2-phenethyl-2-chloroethyl sulfide in liquid and gas phases.

    Science.gov (United States)

    Vorontsov, Alexandre V; Panchenko, Alexander A; Savinov, Evgueni N; Lion, Claude; Smirniotis, Panagiotis G

    2002-12-01

    This work explores the ability of photocatalysis to decontaminate water and air from chemical warfare agent mustard using its simulant 2-phenethyl 2-chloroethyl sulfide (PECES). PECES like mustard slowly dissolves in water with hydrolysis, forming 2-phenethyl 2-hydroxyethyl sulfide (PEHES). Irradiation of TiO2 suspension containing PECES with the unfiltered light of a mercury lamp (lambda > or = 254 nm) decomposed all PECES mostly via photolysis. Reaction under filtered light (lambda > 300 nm) proceeds mainly photocatalytically and requires longer time. Sulfur from starting PECES is completely transformed into sulfuric acid at the end of the reaction. Detected volatile, nonvolatile, surface products, and the suggested scheme of degradation are reported. The main volatile products are styrene and benzaldehyde, nonvolatile--hydroxylated PEHES, surface--2-phenethyl disulfide. Photolysis of PECES produced the same set of volatile products as photocatalysis. Photocatalytic degradation of gaseous PECES in air results in its mineralization but is accompanied by TiO2 deactivation. The highest rate of mineralization with minimum deactivation was observed at about room temperature and a water concentration of 27,500 ppm. No gaseous products except CO2 were detected. The main extracted surface product was styrene. It was concluded that PECES photocatalytic degradation proceeds mainly via C-S bond cleavage and further oxidation of the products. Hydrolysis of the C-S bond was detected only in gas-phase photocatalytic degradation. The quantum efficiency of gas-phase degradation (0.28%) was much higher than that of liquid-phase degradation (0.008%). The results demonstrate the ability of photocatalysis to decontaminate an aqueous and especially an air environment

  1. Molecular simulation of excess isotherm and excess enthalpy change in gas-phase adsorption.

    Science.gov (United States)

    Do, D D; Do, H D; Nicholson, D

    2009-01-29

    We present a new approach to calculating excess isotherm and differential enthalpy of adsorption on surfaces or in confined spaces by the Monte Carlo molecular simulation method. The approach is very general and, most importantly, is unambiguous in its application to any configuration of solid structure (crystalline, graphite layer or disordered porous glass), to any type of fluid (simple or complex molecule), and to any operating conditions (subcritical or supercritical). The behavior of the adsorbed phase is studied using the partial molar energy of the simulation box. However, to characterize adsorption for comparison with experimental data, the isotherm is best described by the excess amount, and the enthalpy of adsorption is defined as the change in the total enthalpy of the simulation box with the change in the excess amount, keeping the total number (gas + adsorbed phases) constant. The excess quantities (capacity and energy) require a choice of a reference gaseous phase, which is defined as the adsorptive gas phase occupying the accessible volume and having a density equal to the bulk gas density. The accessible volume is defined as the mean volume space accessible to the center of mass of the adsorbate under consideration. With this choice, the excess isotherm passes through a maximum but always remains positive. This is in stark contrast to the literature where helium void volume is used (which is always greater than the accessible volume) and the resulting excess can be negative. Our definition of enthalpy change is equivalent to the difference between the partial molar enthalpy of the gas phase and the partial molar enthalpy of the adsorbed phase. There is no need to assume ideal gas or negligible molar volume of the adsorbed phase as is traditionally done in the literature. We illustrate this new approach with adsorption of argon, nitrogen, and carbon dioxide under subcritical and supercritical conditions.

  2. A protocol for detecting and scavenging gas-phase free radicals in mainstream cigarette smoke.

    Science.gov (United States)

    Yu, Long-Xi; Dzikovski, Boris G; Freed, Jack H

    2012-01-02

    Cigarette smoking is associated with human cancers. It has been reported that most of the lung cancer deaths are caused by cigarette smoking (5,6,7,12). Although tobacco tars and related products in the particle phase of cigarette smoke are major causes of carcinogenic and mutagenic related diseases, cigarette smoke contains significant amounts of free radicals that are also considered as an important group of carcinogens(9,10). Free radicals attack cell constituents by damaging protein structure, lipids and DNA sequences and increase the risks of developing various types of cancers. Inhaled radicals produce adducts that contribute to many of the negative health effects of tobacco smoke in the lung(3). Studies have been conducted to reduce free radicals in cigarette smoke to decrease risks of the smoking-induced damage. It has been reported that haemoglobin and heme-containing compounds could partially scavenge nitric oxide, reactive oxidants and carcinogenic volatile nitrosocompounds of cigarette smoke(4). A 'bio-filter' consisted of haemoglobin and activated carbon was used to scavenge the free radicals and to remove up to 90% of the free radicals from cigarette smoke(14). However, due to the cost-ineffectiveness, it has not been successfully commercialized. Another study showed good scavenging efficiency of shikonin, a component of Chinese herbal medicine(8). In the present study, we report a protocol for introducing common natural antioxidant extracts into the cigarette filter for scavenging gas phase free radicals in cigarette smoke and measurement of the scavenge effect on gas phase free radicals in mainstream cigarette smoke (MCS) using spin-trapping Electron Spin Resonance (ESR) Spectroscopy(1,2,14). We showed high scavenging capacity of lycopene and grape seed extract which could point to their future application in cigarette filters. An important advantage of these prospective scavengers is that they can be obtained in large quantities from byproducts of

  3. Conformational preferences of γ-aminobutyric acid in the gas phase and in water

    Science.gov (United States)

    Song, Il Keun; Kang, Young Kee

    2012-09-01

    The conformational study of γ-aminobutyric acid (GABA) has been carried out at the M06-2X/cc-pVTZ level of theory in the gas phase and the SMD M06-2X/cc-pVTZ level of theory in water. In the gas phase, the folded conformation gG1 with gauche- and gauche+ conformations for the Cβsbnd Cα and Cγsbnd Cβ bonds, respectively, is found to be lowest in energy and enthalpy, which can be ascribed to the favored hyperconjugative n → π* interaction between the lone electron pair of the amine nitrogen atom and the Cdbnd O bond of the carboxylic group and the favored antiparallel dipole-dipole interaction between the Nsbnd H bond and the Cdbnd O bond. In addition, the intramolecular hydrogen bonds between the carboxylic group and the amine Nsbnd H group have contributed to stabilize some low-energy conformers. However, the most preferred conformation is found to be tG1 and more stable by 0.4 kcal/mol in ΔG than the conformer gG1, in which the favored entropic term due to the conformational flexibility and the other favored n → σ*, σ → σ*, and π → σ* interactions seem to play a role. The conformational preferences of the neutral GABA calculated by ΔG's are reasonably consistent with the populations deduced from FT microwave spectroscopy in supersonic jets combined with laser ablation. In water, the two folded conformers Gg and gG of the zwitterionic GABA are dominantly populated, each of which has the population of 47%, and the hydrogen bond between the ammonium Nsbnd H group and the lone electron pair of the Csbnd O- group seems to be crucial in stabilizing these conformers. Our calculated result that the folded conformers preferentially exist in water is consistent with the 1H NMR experiments in D2O.

  4. Are cyclopentadienylberyllium, magnesium and calcium hydrides carbon or metal acids in the gas phase?

    Science.gov (United States)

    Hurtado, Marcela; Lamsabhi, Al-Mokhtar; Mó, Otilia; Yáñez, Manuel; Guillemin, Jean-Claude

    2010-05-21

    The structure and bonding of cyclopentadienylberyllium (CpBeH), magnesium (CpMgH), and calcium (CpCaH) hydrides as well as those of their deprotonated species have been investigated by means of B3LYP/6-311+G(3df,2p)//B3LYP/6-311+G(d,p) and B3LYP/6-311+G(3df,2p)//QCISD/6-311+G(d,p) density functional theory (DFT) calculations. The three compounds exhibit C(5v) equilibrium conformations in their ground states. For CpBeH the agreement between the calculated geometry and that determined by MW spectroscopy is excellent. CpMgH and CpCaH can be viewed almost as the result of the interaction between a C₅H₅⁻ anion and a XH(+) (X = Mg, Ca) cation. Conversely, for CpBeH the interaction between the C₅H₅ and the BeH subunits is significantly covalent. These compounds exhibit a significant aromaticity, usually named three-dimension aromaticity, in contrast with the unsubstituted cyclopentadiene compound. The CpBeH derivative behaves as a C acid in the gas phase and is less acidic than cyclopentadiene. More importantly, CpMgH and CpCaH, in spite of the X(+δ)H(-δ) polarity exhibited by the X-H bond in the neutral systems, are predicted to be metal acids in the gas phase. Also surprisingly, both the Mg and the Ca derivatives are stronger acids than the Be analogue, and only slightly weaker acids than cyclopentadiene. This somewhat unexpected result is the consequence of two concomitant facts: the lower dissociation energy of the X-H (X = Mg, Ca) bonds with respect to the C-H bonds, and the significantly high electron affinity of the C₅H₅X* (X = Mg, Ca) radicals.

  5. Dioxygen Binding to Protonated Heme in the Gas Phase, an Intermediate Between Ferric and Ferrous Heme.

    Science.gov (United States)

    Shafizadeh, Niloufar; Soorkia, Satchin; Grégoire, Gilles; Broquier, Michel; Crestoni, Maria-Elisa; Soep, Benoît

    2017-09-27

    With a view to characterizing the influence of the electronic structure of the Fe atom on the nature of its bond with dioxygen (O2 ) in heme compounds, a study of the UV/Vis action spectra and binding energies of heme-O2 molecules has been undertaken in the gas phase. The binding reaction of protonated ferrous heme [Fe(II) -hemeH](+) with O2 has been studied in the gas phase by determining the equilibrium of complexed [Fe(II) -hemeH(O2 )](+) with uncomplexed protonated heme in an ion trap at controlled temperatures. The binding energy of O2 to the Fe atom of protonated ferrous heme was obtained from a van't Hoff plot. Surprisingly, this energy (1540±170 cm(-1) , 18.4±2 kJ mol(-1) ) is intermediate between those of ferric heme and ferrous heme. This result is interpreted in terms of a delocalization of the positive charge over the porphyrin cycle, such that the Fe atom bears a fractional positive charge. The resulting electron distribution on the Fe atom differs notably from that of a purely low-spin ferrous heme [Fe(II) -heme(O2 )] complex, as deduced from its absorption spectrum. It also differs from that of ferric heme [Fe(III) -heme(O2 )](+) , as evidenced by the absorption spectra. Protonated heme creates a specific bond that cannot accommodate strong σ donation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Computational study on hydrolysis of cefotaxime in gas phase and in aqueous solution.

    Science.gov (United States)

    Meliá, Conchín; Ferrer, Silvia; Moliner, Vicent; Tuñón, Iñaki; Bertrán, Juan

    2012-09-15

    We are presenting a theoretical study of the hydrolysis of a β-lactam antibiotic in gas phase and in aqueous solution by means of hybrid quantum mechanics/molecular mechanics potentials. After exploring the potential energy surfaces at semiempirical and density functional theory (DFT) level, potentials of mean force have been computed for the reaction in solution with hybrid PM3/TIP3P calculations and corrections with the B3LYP and M06-2X functionals. Inclusion of the full molecule of the antibiotic, Cefotaxime, in the gas phase molecular model has been demonstrated to be crucial since its carboxylate group can activate a nucleophilic water molecule. Moreover, the flexibility of the substrate implies the existence of a huge number of possible conformers, some of them implying formation of intramolecular hydrogen bond interaction that can determine the energetics of the conformers defining the different states along the reaction profile. The results show PM3 provides results that are in qualitative agreement with DFT calculations. The free energy profiles show a step-wise mechanism that is kinetically determined by the nucleophilic attack of a water molecule activated by the proton transfer to the carboxylate group of the substrate (the first step). However, since the main role of the β-lactamase would be reducing the free energy barrier of the first step, and keeping in mind the barrier obtained from second intermediate to products, population of this second intermediate could be significant and consequently experimentally detected in β-lactamases, as shown in the literature.

  7. Preparation of cold ions in strong magnetic field and its application to gas-phase NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Fuke, K., E-mail: fuke@kobe-u.ac.jp [Institute for Molecular Science (Japan); Ohshima, Y. [Tokyo Institute of Technology, Department of Chemistry (Japan); Tona, M. [Ayabo Co. Fukukama (Japan)

    2015-11-15

    Nuclear Magnetic Resonance (NMR) technique is widely used as a powerful tool to study the physical and chemical properties of materials. However, this technique is limited to the materials in condensed phases. To extend this technique to the gas-phase molecular ions, we are developing a gas-phase NMR apparatus. In this note, we describe the basic principle of the NMR detection for molecular ions in the gas phase based on a Stern-Gerlach type experiment in a Penning trap and outline the apparatus under development. We also present the experimental procedures and the results on the formation and the manipulation of cold ions under a strong magnetic field, which are the key techniques to detect the NMR by the present method.

  8. Preparation of cold ions in strong magnetic field and its application to gas-phase NMR spectroscopy

    Science.gov (United States)

    Fuke, K.; Ohshima, Y.; Tona, M.

    2015-11-01

    Nuclear Magnetic Resonance (NMR) technique is widely used as a powerful tool to study the physical and chemical properties of materials. However, this technique is limited to the materials in condensed phases. To extend this technique to the gas-phase molecular ions, we are developing a gas-phase NMR apparatus. In this note, we describe the basic principle of the NMR detection for molecular ions in the gas phase based on a Stern-Gerlach type experiment in a Penning trap and outline the apparatus under development. We also present the experimental procedures and the results on the formation and the manipulation of cold ions under a strong magnetic field, which are the key techniques to detect the NMR by the present method.

  9. An Overview of Mode of Action and Analytical Methods for Evaluation of Gas Phase Activities of Flame Retardants

    Directory of Open Access Journals (Sweden)

    Khalifah A. Salmeia

    2015-03-01

    Full Text Available The latest techniques used to prove, describe and analyze the gas phase activity of a fire retardant used in polymeric materials are briefly reviewed. Classical techniques, such as thermogravimetric analysis or microscale combustion calorimetry, as well as complex and advanced analytical techniques, such as modified microscale combustion calorimeter (MCC, molecular beam mass spectroscopy and vacuum ultra violet (VUV photoionization spectroscopy coupled with time of flight MS (TOF-MS, are described in this review. The recent advances in analytical techniques help not only in determining the gas phase activity of the flame-retardants but also identify possible reactive species responsible for gas phase flame inhibition. The complete understanding of the decomposition pathways and the flame retardant activity of a flame retardant system is essential for the development of new eco-friendly-tailored flame retardant molecules with high flame retardant efficiency.

  10. Numerical analysis of an impinging jet reactor for the CVD and gas-phase nucleation of titania

    Science.gov (United States)

    Gokoglu, Suleyman A.; Stewart, Gregory D.; Collins, Joshua; Rosner, Daniel E.

    1994-06-01

    We model a cold-wall atmospheric pressure impinging jet reactor to study the CVD and gas-phase nucleation of TiO2 from a titanium tetra-iso-propoxide (TTIP)/oxygen dilute source gas mixture in nitrogen. The mathematical model uses the computational code FIDAP and complements our recent asymptotic theory for high activation energy gas-phase reactions in thin chemically reacting sublayers. The numerical predictions highlight deviations from ideality in various regions inside the experimental reactor. Model predictions of deposition rates and the onset of gas-phase nucleation compare favorably with experiments. Although variable property effects on deposition rates are not significant (approximately 11 percent at 1000 K), the reduction rates due to Soret transport is substantial (approximately 75 percent at 1000 K).

  11. An elementary reaction kinetic model of the gas-phase formation of polychlorinated dibenzofurans from chlorinated phenols

    Energy Technology Data Exchange (ETDEWEB)

    Dellinger, B.; Khachatryan, L. [Louisiana State Univ., Baton Rouge, LA (United States); Asatryan, R. [State Medical Univ., Yerevan (Armenia)

    2004-09-15

    Combustion and thermal processes are generally recognized as the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F or simply ''dioxins'') in the environment. A previously developed, simple mechanism of gas-phase formation of PCDD from chlorinated phenols suggested that the gas-phase formation pathway was too slow to account for concentrations of PCDD observed in full-scale combustors. As a result, most research on formation of PCDD/F in combustion sources focused on surface-mediated formation. In this manuscript, we report the development of a modified model for the purely gas-phase formation of polychlorinated dibenzofurans (PCDFs) that is based on the experimentally observed formation of PCDF from the oxidation of 2,4,6-trichlorophenol (TCP) in the presence of hexane.

  12. LITERATURE REVIEW: HEAT TRANSFER THROUGH TWO-PHASE INSULATION SYSTEMS CONSISTING OF POWDERS IN A CONTINUOUS GAS PHASE

    Science.gov (United States)

    The report, a review of the literature on heat flow through powders, was motivated by the use of fine powder systems to produce high thermal resistivities (thermal resistance per unit thickness). he term "superinsulations" has been used to describe this type of material, which ha...

  13. Gas phase synthesis of non-bundled, small diameter single-walled carbon nanotubes with near-armchair chiralities

    Energy Technology Data Exchange (ETDEWEB)

    Mustonen, K.; Laiho, P.; Kaskela, A.; Zhu, Z.; Reynaud, O.; Houbenov, N.; Tian, Y.; Jiang, H.; Kauppinen, E. I., E-mail: esko.kauppinen@aalto.fi [Department of Applied Physics, Aalto University School of Science, P.O. Box 15100, FI-00076 Aalto (Finland); Susi, T. [Faculty of Physics, University of Vienna, Boltzmanngasse 5, A-1090 Vienna (Austria); Nasibulin, A. G. [Department of Applied Physics, Aalto University School of Science, P.O. Box 15100, FI-00076 Aalto (Finland); Skolkovo Institute of Science and Technology, Nobel str. 3, 143026 (Russian Federation); Saint-Petersburg State Polytechnical University, 29 Polytechniheskaya st., St. Petersburg, 195251 (Russian Federation)

    2015-07-06

    We present a floating catalyst synthesis route for individual, i.e., non-bundled, small diameter single-walled carbon nanotubes (SWCNTs) with a narrow chiral angle distribution peaking at high chiralities near the armchair species. An ex situ spark discharge generator was used to form iron particles with geometric number mean diameters of 3–4 nm and fed into a laminar flow chemical vapour deposition reactor for the continuous synthesis of long and high-quality SWCNTs from ambient pressure carbon monoxide. The intensity ratio of G/D peaks in Raman spectra up to 48 and mean tube lengths up to 4 μm were observed. The chiral distributions, as directly determined by electron diffraction in the transmission electron microscope, clustered around the (n,m) indices (7,6), (8,6), (8,7), and (9,6), with up to 70% of tubes having chiral angles over 20°. The mean diameter of SWCNTs was reduced from 1.10 to 1.04 nm by decreasing the growth temperature from 880 to 750 °C, which simultaneously increased the fraction of semiconducting tubes from 67% to 80%. Limiting the nanotube gas phase number concentration to ∼10{sup 5 }cm{sup −3} prevented nanotube bundle formation that is due to collisions induced by Brownian diffusion. Up to 80% of 500 as-deposited tubes observed by atomic force and transmission electron microscopy were individual. Transparent conducting films deposited from these SWCNTs exhibited record low sheet resistances of 63 Ω/□ at 90% transparency for 550 nm light.

  14. IRMPD action spectroscopy of alkali metal cation-cytosine complexes: effects of alkali metal cation size on gas phase conformation.

    Science.gov (United States)

    Yang, Bo; Wu, R R; Polfer, N C; Berden, G; Oomens, J; Rodgers, M T

    2013-10-01

    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both similar and distinctive spectral features over the range of ~1000-1900 cm(-1). The IRMPD spectra of the Li(+)(cytosine), Na(+)(cytosine), and K(+)(cytosine) complexes are relatively simple but exhibit changes in the shape and shifts in the positions of several bands that correlate with the size of the alkali metal cation. The IRMPD spectra of the Rb(+)(cytosine) and Cs(+)(cytosine) complexes are much richer as distinctive new IR bands are observed, and the positions of several bands continue to shift in relation to the size of the metal cation. The measured IRMPD spectra are compared to linear IR spectra of stable low-energy tautomeric conformations calculated at the B3LYP/def2-TZVPPD level of theory to identify the conformations accessed in the experiments. These comparisons suggest that the evolution in the features in the IRMPD action spectra with the size of the metal cation, and the appearance of new bands for the larger metal cations, are the result of the variations in the intensities at which these complexes can be generated and the strength of the alkali metal cation-cytosine binding interaction, not the presence of multiple tautomeric conformations. Only a single tautomeric conformation is accessed for all five alkali metal cation-cytosine complexes, where the alkali metal cation binds to the O2 and N3 atoms of the canonical amino-oxo tautomer of cytosine, M(+)(C1).

  15. Insights into gas-phase reaction mechanisms of small carbon radicals using isomer-resolved product detection.

    Science.gov (United States)

    Trevitt, Adam J; Goulay, Fabien

    2016-02-17

    For reactive gas-phase environments, including combustion, extraterrestrials atmospheres and our Earth's atmosphere, the availability of quality chemical data is essential for predictive chemical models. These data include reaction rate coefficients and product branching fractions. This perspective overviews recent isomer-resolved production detection experiments for reactions of two of the most reactive gas phase radicals, the CN and CH radicals, with a suite of small hydrocarbons. A particular focus is given to flow-tube experiments using synchrotron photoionization mass spectrometry. Coupled with computational studies and other experiment techniques, flow tube isomer-resolved product detection have provided significant mechanistic details of these radical + neutral reactions with some general patterns emerging.

  16. Method of monitoring photoactive organic molecules in-situ during gas-phase deposition of the photoactive organic molecules

    Science.gov (United States)

    Forrest, Stephen R.; Vartanian, Garen; Rolin, Cedric

    2015-06-23

    A method for in-situ monitoring of gas-phase photoactive organic molecules in real time while depositing a film of the photoactive organic molecules on a substrate in a processing chamber for depositing the film includes irradiating the gas-phase photoactive organic molecules in the processing chamber with a radiation from a radiation source in-situ while depositing the film of the one or more organic materials and measuring the intensity of the resulting photoluminescence emission from the organic material. One or more processing parameters associated with the deposition process can be determined from the photoluminescence intensity data in real time providing useful feedback on the deposition process.

  17. Ab Initio Studies on the Preferred Site of Protonation in Cytisine in the Gas Phase and Water

    Directory of Open Access Journals (Sweden)

    Małgorzata Darowska

    2005-01-01

    Full Text Available Abstract: Ab initio calculations (HF, MP2, DFT for isolated and PCM for solvated molecules were performed for cytisine (1 and its model compounds: N-methyl-2-pyridone (2 and piperidine (3. Among three heteroatomic functions (carbonyl oxygen, pyridone and piperidine nitrogens considered as the possible sites of protonation in 1, surprisingly the carbonyl oxygen takes preferentially the proton in the gas phase whereas in water the piperidine nitrogen is firstly protonated. For model compounds, the piperidine nitrogen in 3 is more basic than the carbonyl oxygen in 2 in both, the gas phase and water.

  18. The structure of geminal imidazolium bis(trifluoromethylsulfonyl)amide ionic liquids: a theoretical study of the gas phase ionic complexes.

    Science.gov (United States)

    Bodo, E; Caminiti, R

    2010-12-02

    In this work we report molecular mechanics and ab initio calculations on the geminal di-imidazolium bis(trifluoromethylsulfonyl)amide ionic liquid in the gas phase. We report the likely energetically preferred geometries of the ionic complex and its main features in terms of charge distribution, electronic density, structure, and energetics. We find that the gas phase structure of the ionic complex is quite compact and that the alkyl chain connecting the two imidazolium charged rings is strongly bent in order to maximize their electrostatic interactions with the two anions.

  19. Gas-phase intramolecular elimination reaction studies of steviol glycosides in positive electrospray and tandem mass spectrometry.

    Science.gov (United States)

    Upreti, Mani; Clos, John F; Somayajula, Kasi V; Milanowski, Dennis J; Mocek, Ulla; Dubois, Grant E; Prakash, Indra

    2009-01-01

    This paper reports the first study of the gas-phase intramolecular elimination reaction of steviol glycosides in positive electrospray mass spectrometry. The observed glycosylated product ions are proposed to be formed via an intramolecular elimination of sugar units from the parent molecule ion. It was further proven by MS/MS studies and deuterium labeling experiments with one of the steviol glycosides, rebaudioside A. These mass spectrometric results confirmed that the new glycosylated product ions observed are most likely formed by the combination of glucose moieties (Glu) II-IV and Glu I via a gas-phase intramolecular elimination reaction.

  20. Removal of gas-phase ammonia and hydrogen sulfide using photocatalysis, nonthermal plasma, and combined plasma and photocatalysis at pilot scale.

    Science.gov (United States)

    Maxime, Guillerm; Amine, Assadi Aymen; Abdelkrim, Bouzaza; Dominique, Wolbert

    2014-11-01

    This study focuses on the removal of gas-phase ammonia (NH3) and hydrogen sulfide (H2S) in a continuous reactor. Photocatalysis and surface dielectric barrier discharge (SDBD) plasma are studied separately and combined. Though the removal of volatile organic compounds by coupling plasma and photocatalysis has been reported on a number of studies in laboratory scale, this is as far as we know the first time that it is used to remove inorganic malodorous pollutants. While each separate process is able to degrade ammonia and hydrogen sulfide, a synergetic effect appears when they are combined at a pilot scale, leading to removal capacity higher than the sum of each separate process. The removal capacity is higher when the gas circulates at a higher flow rate and when pollutant concentration is higher. The presence of water vapor in the gas is detrimental to the efficiency of the process. Operating conditions also influence the production of nitrogen oxides and ozone.

  1. Native electrospray ionization and electron-capture dissociation for comparison of protein structure in solution and the gas phase.

    Science.gov (United States)

    Zhang, Hao; Cui, Weidong; Gross, Michael L

    2013-11-15

    The importance of protein and protein-complex structure motivates improvements in speed and sensitivity of structure determination in the gas phase and comparison with that in solution or solid state. An opportunity for the gas phase measurement is mass spectrometry (MS) combined with native electrospray ionization (ESI), which delivers large proteins and protein complexes in their near-native states to the gas phase. In this communication, we describe the combination of native ESI, electron-capture dissociation (ECD), and top-down MS for exploring the structures of ubiquitin and cytochrome c in the gas phase and their relation to those in the solid-state and solution. We probe structure by comparing the protein's flexible regions, as predicted by the B-factor in X-ray crystallography, with the ECD fragments. The underlying hypothesis is that maintenance of structure gives fragments that can be predicted from B-factors. This strategy may be applicable in general when X-ray structures are available and extendable to the study of intrinsically disordered proteins.

  2. Chemical Composition of Gas Phase and Secondary Organic Aerosol from Aromatic Precursors Produced in a Smog Chamber

    Energy Technology Data Exchange (ETDEWEB)

    Sax, M. [ETH Zuerich and PSI (Switzerland); Kalberer, M. [ETH Zuerich (Switzerland); Zenobi, R. [ETH Zuerich (Switzerland); Paulsen, D.; Baltensperger, U.

    2004-03-01

    Reaction products formed during photooxidation of aromatic compounds contribute to secondary organic aerosol (SOA) mass. In this study we performed experiments with 1,3,5-trimethylbenzene (135TMB) in the PSI smog chamber to study the formation and composition of SOA. We used different techniques to analyze the aerosol and the gas phase. (author)

  3. [Study on the gas-phase reaction of alpha-pinene with ozone by LP-FTIR].

    Science.gov (United States)

    Liu, Zhao-rong; Hu, Di

    2004-07-01

    The gas-phase reaction of a-pinene with ozone was tailed by LP-FTIR under 1.0 x 10(5) Pa and (296 +/- 3)K. The spectra were analyzed and a preliminary predication of the possible products was made. Then the mechanism of this reaction was extrapolated according to the IR data.

  4. Activation of propane C-H and C-C bonds by gas-phase Pt atom: a theoretical study

    National Research Council Canada - National Science Library

    Li, Fang-Ming; Yang, Hua-Qing; Ju, Ting-Yong; Li, Xiang-Yuan; Hu, Chang-Wei

    2012-01-01

    The reaction mechanism of the gas-phase Pt atom with C(3)H(8) has been systematically investigated on the singlet and triplet potential energy surfaces at CCSD(T)//BPW91/6-311++G(d, p), Lanl2dz level...

  5. Gas-phase hydrogen/deuterium exchange in a traveling wave ion guide for the examination of protein conformations.

    Science.gov (United States)

    Rand, Kasper D; Pringle, Steven D; Murphy, James P; Fadgen, Keith E; Brown, Jeff; Engen, John R

    2009-12-15

    Accumulating evidence suggests that solution-phase conformations of small globular proteins and large molecular protein assemblies can be preserved for milliseconds after electrospray ionization. Thus, the study of proteins in the gas phase on this time scale is highly desirable. Here we demonstrate that a traveling wave ion guide (TWIG) of a Synapt mass spectrometer offers a highly suitable environment for rapid and efficient gas-phase hydrogen/deuterium exchange (HDX). Gaseous ND(3) was introduced into either the source TWIG or the TWIG located just after the ion mobility cell, such that ions underwent HDX as they passed through the ND(3) on the way to the time-of-flight analyzer. The extent of deuterium labeling could be controlled by varying the quantity of ND(3) or the speed of the traveling wave. The gas-phase HDX of model peptides corresponded to labeling of primarily fast exchanging sites due to the short labeling times (ranging from 0.1 to 10 ms). In addition to peptides, gas-phase HDX of ubiquitin, cytochrome c, lysozyme, and apomyoglobin were examined. We conclude that HDX of protein ions in a TWIG is highly sensitive to protein conformation, enables the detection of conformers present on submilliseconds time scales, and can readily be combined with ion mobility spectrometry.

  6. Lateral gas phase diffusion length of boron atoms over Si/B surfaces during CVD of pure boron layers

    NARCIS (Netherlands)

    Mohammadi, V.; Nihtianov, S.

    2016-01-01

    The lateral gas phase diffusion length of boron atoms, LB, along silicon and boron surfaces during chemical vapor deposition(CVD) using diborane (B2H6) is reported. The value of LB is critical for reliable and uniform boron layer coverage. The presented information was obtained experimentally and co

  7. SITE PROGRAM DEMONSTRATION ECO LOGIC INTERNATIONAL GAS-PHASE CHEMICAL REDUCTION PROCESS, BAY CITY, MICHIGAN TECHNOLOGY EVALUATION REPORT

    Science.gov (United States)

    The SITE Program funded a field demonstration to evaluate the Eco Logic Gas-Phase Chemical Reduction Process developed by ELI Eco Logic International Inc. (ELI), Ontario, Canada. The Demonstration took place at the Middleground Landfill in Bay City, Michigan using landfill wa...

  8. Near edge X-ray absorption mass spectrometry of gas phase proteins: the influence of protein size

    NARCIS (Netherlands)

    Egorov, Dmitrii; Schwob, Lucas; Lalande, Mathieu; Hoekstra, Ronnie; Schlathölter, Thomas

    2016-01-01

    Multiply protonated peptides and proteins in the gas phase can respond to near edge X-ray absorption in three different ways: (i) non dissociative ionization and ionization accompanied by loss of small neutrals, both known to dominate for proteins with masses in the 10 kDa range. (ii) Formation of i

  9. Gas-phase synthesis of hexagonal and cubic phases of aluminum nitride: A method and its advantages

    Science.gov (United States)

    Kudyakova, V. S.; Bannikov, V. V.; Elagin, A. A.; Shishkin, R. A.; Baranov, M. V.; Beketov, A. R.

    2016-03-01

    Experimental results obtained in AlN synthesis by the high-temperature gas-phase method and analysis of reaction products phase composition are briefly described. It is demonstrated for the first time that dispersed aluminum nitride can be synthesized by this method from AlF3 in both hexagonal and cubic modifications.

  10. Lateral gas phase diffusion length of boron atoms over Si/B surfaces during CVD of pure boron layers

    NARCIS (Netherlands)

    Mohammadi, V.; Nihtianov, S.

    2016-01-01

    The lateral gas phase diffusion length of boron atoms, LB, along silicon and boron surfaces during chemical vapor deposition(CVD) using diborane (B2H6) is reported. The value of LB is critical for reliable and uniform boron layer coverage. The presented information was obtained experimentally and co

  11. Effects of Gas-Phase Adsorption air purification on passengers and cabin crew in simulated 11-hour flights

    DEFF Research Database (Denmark)

    Strøm-Tejsen, Peter; Zukowska, Daria; Fang, Lei

    2006-01-01

    .4 and 3.3 L/s per person), with and without a Gas-Phase Adsorption (GPA) unit in the re-circulated air system. Objective physical and physiological measurements and subjective human assessments of symptom intensity were obtained. The GPA unit provided advantages with no apparent disadvantages....

  12. Advantages for passengers and cabin crew of operating a Gas-Phase Adsorption air purifier in 11-h simulated flights

    DEFF Research Database (Denmark)

    Strøm-Tejsen, Peter; Zukowska, Daria; Fang, Lei

    2008-01-01

    Experiments were carried out in a 3-row, 21-seat section of a simulated aircraft cabin installed in a climate chamber to evaluate the extent to which passengers’ perception of cabin air quality is affected by the operation of a Gas-Phase Adsorption (GPA) purification unit. A total of 68 subjects...

  13. Enantiomeric Excess Determination for Monosaccharides Using Chiral Transmission to Cold Gas-Phase Tryptophan in Ultraviolet Photodissociation

    Science.gov (United States)

    Fujihara, Akimasa; Maeda, Naoto; Doan, Thuc N.; Hayakawa, Shigeo

    2017-02-01

    Chiral transmission between monosaccharides and amino acids via photodissociation in the gas phase was examined using a tandem mass spectrometer fitted with an electrospray ionization source and a cold ion trap in order to investigate the origin of the homochirality of biomolecules in molecular clouds. Ultraviolet photodissociation mass spectra of cold gas-phase noncovalent complexes of the monosaccharide enantiomers glucose (Glc) and galactose (Gal) with protonated l-tryptophan H+( l-Trp) were obtained by photoexcitation of the indole ring of l-Trp. l-Trp dissociated via Cα-Cβ bond cleavage when noncovalently complexed with d-Glc; however, no dissociation of l-Trp occurred in the homochiral H+( l-Trp)( l-Glc) noncovalent complex, where the energy absorbed by l-Trp was released through the evaporation of l-Glc. This enantioselective photodissociation of Trp was due to the transmission of chirality from Glc to Trp via photodissociation in the gas-phase noncovalent complexes, and was applied to the quantitative chiral analysis of monosaccharides. The enantiomeric excess of monosaccharides in solution could be determined by measuring the relative abundance of the two product ions in a single photodissociation mass spectrum of the cold gas-phase noncovalent complex with H+( l-Trp), and by referring to the linear relationships derived in this work.

  14. Density functional theory study of 1:1 glycine–water complexes in the gas phase and in solution

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    We present a systematic study of 1:1 glycine-water complexes involving all possible glycine conformers. The complex geometries are fully optimized for the first time both in the gas phase and in solution using three DFT methods (B3LYP, PBE1PBE, X3LYP) and the MP2 method. We calculate the G3 energies and use them as the reference data to gauge hydrogen bond strength in the gas phase. The solvent effects are treated via the integral equation formalism-polarizable continuum model (IEF-PCM). Altogether, we locate fifty-two unique nonionized (N) structures and six zwitterionic (Z) structures in the gas phase, and fifty-five N structures and thirteen Z structures in solution. Both correlation and solvation are shown to be important in geometry determination. We found that in the gas phase, a water molecule binds more strongly to the carboxylic acid group of glycine than to its amine group, whereas in solution phase the reverse is true. The most stable Z structure is isoenergetic with the most stable N structure.

  15. c2d Spitzer IRS spectra of embedded low-mass young stars : gas-phase emission lines

    NARCIS (Netherlands)

    Lahuis, F.; van Dishoeck, E. F.; Jorgensen, J. K.; Blake, G. A.; Evans, N. J.

    2010-01-01

    Context. A survey of mid-infrared gas-phase emission lines of H(2), H(2)O and various atoms toward a sample of 43 embedded low-mass young stars in nearby star-forming regions is presented. The sources are selected from the Spitzer "Cores to Disks" (c2d) legacy program. Aims. The environment of embed

  16. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    NARCIS (Netherlands)

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.

    2013-01-01

    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both simi

  17. Development and validation of a portable gas phase standard generation and calibration system for volatile organic compounds

    Science.gov (United States)

    P. Veres; J. B. Gilman; J. M. Roberts; W. C. Kuster; C. Warneke; I. R. Burling; J. de Gouw

    2010-01-01

    We report on the development of an accurate, portable, dynamic calibration system for volatile organic compounds (VOCs). The Mobile Organic Carbon Calibration System (MOCCS) combines the production of gas-phase VOC standards using permeation or diffusion sources with quantitative total organic carbon (TOC) conversion on a palladium surface to CO2 in the presence of...

  18. Experimental determination of the static equivalent pressures of gas phase detonations in pipes and comparison with numerical models

    NARCIS (Netherlands)

    Schildberg, H.P.; Smeulers, J.P.M.; Pape, G.

    2013-01-01

    In order to determine the effective load of gas phase detonations on pipe walls ("static equivalent pressure"), comprehensive experiments have been conducted in 48.3×2.6 and 114.3×3.6 pipes (outer diameter [mm] x wall thickness [mm]), in which deflagrative explosions of stoichiometric C2H4/O2/N2-mix

  19. Thermal degradation events as health hazards: Particle vs gas phase effects, mechanistic studies with particles

    Science.gov (United States)

    Oberdörster, G.; Ferin, J.; Finkelstein, J.; Soderholm, S.

    Exposure to thermal degradation products arising from fire or smoke could be a major concern for manned space missions. Severe acute lung damage has been reported in people after accidental exposure to fumes from plastic materials, and animal studies revealed the extremely high toxicity of freshly generated fumes whereas a decrease in toxicity of aged fumes has been found. This and the fact that toxicity of the freshly generated fumes can be prevented with filters raises the question whether the toxicity may be due to the particulate rather than the gas phase components of the thermodegradation products. Indeed, results from recent studies implicate ultrafine particles (particle diameter in the nm range) as potential severe pulmonary toxicants. We have conducted a number of in vivo (inhalation and instillation studies in rats) and in vitro studies to test the hypothesis that ultrafine particles possess an increased potential to injure the lung compared to larger-sized particles. We used as surrogate particles ultrafine TiO 2 particles (12 and 20 nm diameter). Results in exposed rats showed that the ultrafine TiO 2 particles not only induce a greater acute inflammatory reaction in the lung than larger-sized TiO 2 particles, but can also lead to persistent chronic effects, as indicated by an adverse effect on alveolar macrophage mediated clearance function of particles. Release of mediators from alveolar macrophages during phagocytosis of the ultrafine particles and an increased access of the ultrafine particles to the pulmonary interstitium are likely factors contributing to their pulmonary toxicity. In vitro studies with lung cells (alveolar macrophages) showed, in addition, that ultrafine TiO 2 particles have a greater potential to induce cytokines than larger-sized particles. We conclude from our present studies that ultrafine particles have a significant potential to injure the lung and that their occurrence in thermal degradation events can play a major role in

  20. Substituent effects on the gas-phase fragmentation reactions of sulfonium ion containing peptides.

    Science.gov (United States)

    Sierakowski, James; Amunugama, Mahasilu; Roberts, Kade D; Reid, Gavin E

    2007-01-01

    The multistage mass spectrometric (MS/MS and MS3) gas-phase fragmentation reactions of methionine side-chain sulfonium ion containing peptides formed by reaction with a series of para-substituted phenacyl bromide (XBr where X=CH2COC6H4R, and R=--COOH, --COOCH3, --H, --CH3 and --CH2CH3) alkylating reagents have been examined in a linear quadrupole ion trap mass spectrometer. MS/MS of the singly (M+) and multiply ([M++nH](n+1)+) charged precursor ions results in exclusive dissociation at the fixed charge containing side chain, independently of the amino acid composition and precursor ion charge state (i.e., proton mobility). However, loss of the methylphenacyl sulfide side-chain fragment as a neutral versus charged (protonated) species was observed to be highly dependent on the proton mobility of the precursor ion, and the identity of the phenacyl group para-substituent. Molecular orbital calculations were performed at the B3LYP/6-31+G** level of theory to calculate the theoretical proton affinities of the neutral side-chain fragments. The log of the ratio of neutral versus protonated side-chain fragment losses from the derivatized side chain were found to exhibit a linear dependence on the proton affinity of the side-chain fragmentation product, as well as the proton affinities of the peptide product ions. Finally, MS3 dissociation of the nominally identical neutral and protonated loss product ions formed by MS/MS of the [M++H]2+ and [M++2H]3+ precursor ions, respectively, from the peptide GAILM(X)GAILK revealed significant differences in the abundances of the resultant product ions. These results suggest that the protonated peptide product ions formed by gas-phase fragmentation of sulfonium ion containing precursors in an ion trap mass spectrometer do not necessarily undergo intramolecular proton 'scrambling' prior to their further dissociation, in contrast to that previously demonstrated for peptide ions introduced by external ionization sources.

  1. On-line monitoring of gas-phase bioreactors for biogas treatment: hydrogen sulfide and sulfide analysis by automated flow systems

    Energy Technology Data Exchange (ETDEWEB)

    Redondo, Rosa; Cunha Machado, Vinicius; Lafuente, Javier; Gabriel, David [Universitat Autonoma de Barcelona, Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria (ETSE), Bellaterra (Spain); Baeza, Mireia [Edifici C-Nord, Universitat Autonoma de Barcelona, Grup de Sensors i Biosensors, Departament de Quimica, Facultat de Ciencies, Bellaterra (Spain)

    2008-06-15

    Biogas is produced by biological processes under anaerobic conditions and may contain up to 20,000 ppm{sub v} hydrogen sulfide (H{sub 2}S), a corrosive substance that attacks power engines and can affect the health of the industrial staff. H{sub 2}S must be removed from the biogas, especially in co-generation facilities where the biogas is burnt for energy production. Nowadays, biofiltration is being studied and considered as an interesting alternative for removing H{sub 2}S from the biogas besides classical chemical processes. The novelty of this work is the design and construction of an automated H{sub 2}S on-line analyser to assess the composition of the liquid and gas phases of gas-phase bioreactors. The analyser is made of two parallel flow configurations which share the same detection device. The first configuration is a single-channel flow injection analyser (FIA) to detect S{sup 2-} in the liquid phase. The second configuration is a continuous flow analyser (CFA) with a gaseous diffusion step (GD-CFA) for detecting H{sub 2}S in the gas phase. The diffusion step enables separation of the H{sub 2}S{sub (g)} from the sample and its conversion into a detectable chemical species (S{sup 2-}). S{sup 2-} detection was performed with an Ag{sub 2}S ion-selective electrode (ISE) selective to S{sup 2-}{sub (aq)}. The main response parameters of the FIA system are a linear range between 3 x 10{sup -5} and 1 x 10{sup -1} mol L{sup -1} S{sup 2-} (0.61-3,200 mg L{sup -1}), with a sensitivity of 27.9 mV decade{sup -1} and a detection limit of 1.93 x 10{sup -5} mol L{sup -1} S{sup 2-}. The GD-CFA configuration presents a linear range between 400 and 10,000 ppm{sub v} H{sub 2}S{sub (g)} with a sensitivity of 26.1 mV decade{sup -1} and a detection limit of 245 ppm{sub v} H{sub 2}S. The proposed analyser was used by analysing real gas and liquid samples with optimal results at a full-scale biotrickling filter for biogas treatment at a municipal wastewater treatment plant. (orig.)

  2. Effects of cold atmospheric gas phase plasma on anthocyanins and color in pomegranate juice.

    Science.gov (United States)

    Bursać Kovačević, Danijela; Putnik, Predrag; Dragović-Uzelac, Verica; Pedisić, Sandra; Režek Jambrak, Anet; Herceg, Zoran

    2016-01-01

    The aim of the study was to evaluate effects of cold atmospheric gas phase plasma on anthocyanins and color in pomegranate juice. Outcomes of plasma treatment were observed at different operating conditions: (i) treatment time (3, 5, 7 min), (ii) treated juice volume (3, 4, 5 cm(3)), and (iii) gas flow (0.75, 1, 1.25 dm(3)/min). The greatest anthocyanin stability was found at: 3 min treatment time, 5 cm(3) sample volume, and 0.75 dm(3)/min gas flow. Plasma treatment yielded higher anthocyanin content from 21% to 35%. Multivariate analysis showed that total color change was not associated with sample volume and treatment time, however it declined with increased gas flow. The change of color increased in comparison treated vs. untreated pomegranate juice. Constructed mathematical equation confirmed that increase of anthocyanin content increased with gas flow, sample volume and change in color. In summary, this study showed that plasma treatment had positive influences on anthocyanins stability and color change in cloudy pomegranate juice.

  3. The ozonizer discharge as a gas-phase advanced oxidation process

    Energy Technology Data Exchange (ETDEWEB)

    Rosocha, L.A.

    1997-09-01

    In the past several years, there has been increased interest in gas-phase pollution control arising from a larger body of environmental regulations and a greater respect for the environment. One promising class of pollution-control technologies is that called advanced oxidation processes (AOPs). Ozonizers have been used for over a century in water treatment and for about two decades in advanced oxidation. Ozonizers are fundamentally based on non-thermal plasmas, which are useful for generating reactive species (free radicals) in gas streams. Because radical-attack reaction rate constants are very large for many chemical species, entrained pollutants are readily decomposed by these radicals. Non-thermal plasmas can generate both oxidative and reductive radicals; therefore, they show promise for treating a wide variety of pollutants. However, this application is only about a decade old, so more work is needed for optimizing and commercializing the process. This paper is intended to serve as an introduction to the subject of pollutant decomposition with the nonthermal plasmas generated by ozonizer discharges. Basic plasma and decomposition chemistry, laboratory experiments, and example applications are discussed.

  4. Catalytic Properties of Mesoporous Silica (FSM-16) for Beckmann Rearrangement of Cyclohexanone Oxime in Gas Phase

    Energy Technology Data Exchange (ETDEWEB)

    Nakajima, T. [Shinshu Univ, Nagano (Japan). Department of Chemistry and Material Engineering Facutly of Engineering; Nakajima, T. [Iiyama Electric Co. Ltd., Nagano (Japan); Mishima, S. [Shinshu Univ, Nagano (Japan). Cooperative Research Center

    1997-08-10

    Catalytic properties of FSM-16 (porous silica with the honeycomb structure of uniform mesopores) were investigated for Beckmann rearrangement of cyclohexanone oxime in gas phase at 523-623 K, and were compared with those of other typical solid acid catalysts. FSM-16 was found to be a long-life catalyst and exhibited higher conversion of the oxime than silica-alumina, H-ZSM-5, Na-ZSM-5, HX-zeolite, and {gamma}-alumina. Selectivity for {epsilon}-caprolactam of FSM-16 was 42-25%, which was lower than that of H-ZSM-5 (89%), silica-alumina (77%), and HX-zeolite (74%). The product composition given by FSM-16 was very similar to that by silica gel. FSM-16, which was impregnated with a solution of aluminum nitrate and then calcined at 823 K, exhibited a higher selectivity (54%) for {epsilon}-caprolactam than an original one. The activity of FSM-16 was remarkably decreased when the catalyst was calcined at 1073 K or above. However, the selectivity for {epsilon}-caprolactam scarcely changed. 10 refs., 4 figs., 1 tab.

  5. Advanced Laser-Based Techniques for Gas-Phase Diagnostics in Combustion and Aerospace Engineering.

    Science.gov (United States)

    Ehn, Andreas; Zhu, Jiajian; Li, Xuesong; Kiefer, Johannes

    2017-03-01

    Gaining information of species, temperature, and velocity distributions in turbulent combustion and high-speed reactive flows is challenging, particularly for conducting measurements without influencing the experimental object itself. The use of optical and spectroscopic techniques, and in particular laser-based diagnostics, has shown outstanding abilities for performing non-intrusive in situ diagnostics. The development of instrumentation, such as robust lasers with high pulse energy, ultra-short pulse duration, and high repetition rate along with digitized cameras exhibiting high sensitivity, large dynamic range, and frame rates on the order of MHz, has opened up for temporally and spatially resolved volumetric measurements of extreme dynamics and complexities. The aim of this article is to present selected important laser-based techniques for gas-phase diagnostics focusing on their applications in combustion and aerospace engineering. Applicable laser-based techniques for investigations of turbulent flows and combustion such as planar laser-induced fluorescence, Raman and Rayleigh scattering, coherent anti-Stokes Raman scattering, laser-induced grating scattering, particle image velocimetry, laser Doppler anemometry, and tomographic imaging are reviewed and described with some background physics. In addition, demands on instrumentation are further discussed to give insight in the possibilities that are offered by laser flow diagnostics.

  6. Gas phase recovery of hydrogen sulfide contaminated polymer electrolyte membrane fuel cells

    Science.gov (United States)

    Kakati, Biraj Kumar; Kucernak, Anthony R. J.

    2014-04-01

    The effect of hydrogen sulfide (H2S) on the anode of a polymer electrolyte membrane fuel cell (PEMFC) and the gas phase recovery of the contaminated PEMFC using ozone (O3) were studied. Experiments were performed on fuel cell electrodes both in an aqueous electrolyte and within an operating fuel cell. The ex-situ analyses of a fresh electrode; a H2S contaminated electrode (23 μmolH2S cm-2); and the contaminated electrode cleaned with O3 shows that all sulfide can be removed within 900 s at room temperature. Online gas analysis of the recovery process confirms the recovery time required as around 720 s. Similarly, performance studies of an H2S contaminated PEMFC shows that complete rejuvenation occurs following 600-900 s O3 treatment at room temperature. The cleaning process involves both electrochemical oxidation (facilitated by the high equilibrium potential of the O3 reduction process) and direct chemical oxidation of the contaminant. The O3 cleaning process is more efficient than the external polarization of the single cell at 1.6 V. Application of O3 at room temperature limits the amount of carbon corrosion. Room temperature O3 treatment of poisoned fuel cell stacks may offer an efficient and quick remediation method to recover otherwise inoperable systems.

  7. Aerobic oxidation of cyclohexene catalyzed by NiO/MCM-41 nanocomposites in the gas phase

    Indian Academy of Sciences (India)

    Amin Ebadi; Majid Mozaffari; Sanaz Shojaei

    2014-07-01

    The nanoparticles of NiO supported on mesoporous MCM-41 were synthesized and characterized with X-ray diffraction (XRD) and transmission electron microscopy (TEM). In this study, catalytic activities of the supported NiO nanoparticles for oxidation of cyclohexene to 2-cyclohexene-1-ol and 2-cyclohexene-1-one with air in the gas phase were considered. These nanoparticles of NiO supported on mesoporous MCM-41 were effective catalysts in a temperature range of 220-310°C at 1 atm of air. Under these reaction conditions, the activity of the catalysts decreases in the following order: 5 wt.% NiO/MCM-41 > 7.5 wt.% NiO/MCM-41 > 2.5 wt.% NiO/MCM-41. With 5 wt.% NiO supported on mesoporous MCM-41 and under our experimental conditions, the conversion percent of cyclohexene is 62.3% with 65.9% selectivity of 2-cyclohexene-1-ol + 2-cyclohexene-1-one and 12.2% cyclohexadiene at 280°C. To achieve higher conversion of cyclohexene and better selectivity towards 2-cyclohexene-1-ol + 2-cyclohexene-1-one, factors such as reaction temperature, loading amount of nickel oxide and space velocity were studied, and optimized conditions were investigated.

  8. Oxidation of methanol to formaldehyde on supported vanadium oxide catalysts compared to gas phase molecules.

    Science.gov (United States)

    Döbler, Jens; Pritzsche, Marc; Sauer, Joachim

    2005-08-10

    The oxidation of methanol to formaldehyde on silica supported vanadium oxide is studied by density functional theory. For isolated vanadium oxide species silsesquioxane-type models are adopted. The first step is dissociative adsorption of methanol yielding CH3O(O=)V(O-)2 surface complexes. This makes the O=V(OCH3)3 molecule a suited model system. The rate-limiting oxidation step involves hydrogen transfer from the methoxy group to the vanadyl oxygen atom. The transition state is biradicaloid and needs to be treated by the broken-symmetry approach. The activation energies for O=V(OCH3)3 and the silsesquioxane surface model are 147 and 154 kJ/mol. In addition, the (O=V(OCH3)3)(2) dimer (a model for polymeric vanadium oxide species) and the O=V(OCH3)3(*+) radical cation are studied. For the latter the barrier is only 80 kJ/mol, indicating a strong effect of the charge on the energy profile of the reaction and questioning the significance of gas-phase cluster studies for understanding the activity of supported oxide catalysts.

  9. Detection and quantification of gas-phase oxidized mercury compounds by GC/MS

    Science.gov (United States)

    Jones, Colleen P.; Lyman, Seth N.; Jaffe, Daniel A.; Allen, Tanner; O'Neil, Trevor L.

    2016-05-01

    Most mercury pollution is emitted to the atmosphere, and the location and bioavailability of deposited mercury largely depends on poorly understood atmospheric chemical reactions that convert elemental mercury into oxidized mercury compounds. Current measurement methods do not speciate oxidized mercury, leading to uncertainty about which mercury compounds exist in the atmosphere and how oxidized mercury is formed. We have developed a gas chromatography/mass spectrometry (GC-MS)-based system for identification and quantification of atmospheric oxidized mercury compounds. The system consists of an ambient air collection device, a thermal desorption module, a cryofocusing system, a gas chromatograph, and an ultra-sensitive mass spectrometer. It was able to separate and identify mercury halides with detection limits low enough for ambient air collection (90 pg), but an improved ambient air collection device is needed. The GC/MS system was unable to quantify HgO or Hg(NO3)2, and data collected cast doubt upon the existence of HgO in the gas phase.

  10. Gas phase UV spectrum of a Cu(II)-bis(benzene) sandwich complex: experiment and theory.

    Science.gov (United States)

    Ma, Lifu; Koka, Joseph; Stace, Anthony J; Cox, Hazel

    2014-11-13

    Photofragmentation with tunable UV radiation has been used to generate a spectrum for the copper-bis(benzene) complex, [Cu(C6H6)2](2+), in the gas phase. The ions were held in an ion trap where their temperature was reduced to ∼150 K, whereby the spectrum revealed two broad features at ∼38,200 and ∼45,700 cm(-1). Detailed calculations using density functional theory (DFT) show the complex can occupy three minimum energy structures with C2v and C2 (staggered and eclipsed) symmetries. Adiabatic time-dependent DFT (TDDFT) has been used to identify electronic transitions in [Cu(benzene)2](2+), and the calculations show these to fall into two groups that are in excellent agreement with the experimental data. However, the open-shell electronic configuration of Cu(2+) (d(9)) may give rise to excited states with double-excitation character, and the single-excitation adiabatic TDDFT treatment leads to extensive spin contamination. By quantifying the extent of spin contamination and allowing for the inclusion of a small percentage (∼10%), the theory can provide quantitative agreement with the experimental data.

  11. Gas phase propylene epoxidation over Au supported on titanosilicates with different Ti chemical environments

    Science.gov (United States)

    Chen, Xuan-Ye; Chen, Shi-Long; Jia, Ai-Pin; Lu, Ji-Qing; Huang, Wei-Xin

    2017-01-01

    Three Ti-containing porous materials - a mesoporous Ti-MCM-41 with distorted tetrahedral framework Ti sites (denoted as Ti-MCM-41-C), a microporous titanium silicate (TS-1) with tetrahedral framework Ti sites and a hybrid Ti-MCM-41 containing TS-1 microstructure (denoted as Ti-MCM-41-H) were used to prepare supported Au catalysts for gas phase propylene epoxidation in the presence of H2 and O2. Both catalyst structures and catalytic reaction kinetics were investigated in detail. The kinetic results show that the apparent activation energies for both PO and CO2 formation follow the order of Au/Ti-MCM-41-C Au/TS-1 > Au/Ti-MCM-41-C, in consistence with the order of propylene conversion rate, and the adsorption stability follows the order of Au/TS-1 > Au/Ti-MCM-41-H > Au/Ti-MCM-41-C, in consistence with the order of apparent activation energy. These results demonstrated that the adsorption strength of propylene on the titanosilicates supports strongly affected the catalytic behavior, and implied that the support with balanced defective Ti sites and mesoporous/microporous structure may be a promising approach in the preparation of high-performance supported Au catalysts.

  12. Some insights into formamide formation through gas-phase reactions in the interstellar medium

    Energy Technology Data Exchange (ETDEWEB)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio, E-mail: predondo@qf.uva.es [Computational Chemistry Group, Departamento de Química Física, Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid (Spain)

    2014-01-10

    We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH{sub 3}{sup +}, NH{sub 4}{sup +}, NH{sub 3}OH{sup +}, and NH{sub 2}OH{sup +}) and neutral molecules having one carbonyl group (H{sub 2}CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

  13. Repetitively sampled time-of-flight mass spectrometry for gas-phase kinetics studies

    Science.gov (United States)

    Fockenberg, Christopher; Bernstein, Herbert J.; Hall, Gregory E.; Muckerman, James T.; Preses, Jack M.; Sears, Trevor J.; Weston, Ralph E.

    1999-08-01

    An apparatus has been constructed to study radical-radical reactions in the gas phase. It consists of a tubular quartz reactor in which radicals are produced by flash photolysis using an excimer laser as light source. The composition of the gas mixture is analyzed in situ by photoionizing sampled gases using the vacuum ultraviolet emission of a hollow cathode lamp and subsequent time-of-flight mass spectrometry. A simple arrangement of grids at the entrance to the flight tube is used to interrupt the constant flux of ions by application of a combination of constant and pulsed voltages. Individual mass spectra can be taken at a repetition rate of around 20 kHz following each photolysis event. Signal counts from a specified number of consecutive mass spectra are fed into a 2 GHz multiscaler and accumulated as a sampling-time-indexed series of mass spectra. This allows simultaneous observation of the concentrations of multiple transient or stable species on a millisecond time scale. To achieve a suitable signal-to-noise ratio, signals were typically accumulated over several tens of thousands of laser shots at a pulse rate of 10-15 Hz.

  14. How does deposition of gas phase species affect pH at frozen salty interfaces?

    Directory of Open Access Journals (Sweden)

    S. N. Wren

    2012-11-01

    Full Text Available Chemical processes occurring on snow and ice surfaces play an important role in controlling the oxidative capacity of the overlying atmosphere. However, efforts to gain a better, mechanistic understanding of such processes are impeded by our poor understanding of the chemical nature of the air-ice interface. Here we use glancing-angle laser induced fluorescence in conjunction with harmine – a surface-active, pH-sensitive fluorescent dye – to investigate how the nature of the ice, whether frozen freshwater, salt water or seawater, influences pH changes at the surface. Deposition of HCl(g leads to a very different pH response at the frozen freshwater surface than at the frozen salt water surface indicating that these two surfaces present different chemical environments. Importantly, the sea ice surface is buffered against pH changes arising from deposition of gas phase species. These results have important implications for understanding pH-sensitive processes occurring at the air-ice boundary, such as bromine activation.

  15. Surface waters as a sink and source of atmospheric gas phase ethanol.

    Science.gov (United States)

    Avery, G Brooks; Foley, Laura; Carroll, Angela L; Roebuck, Jesse Alan; Guy, Amanda; Mead, Ralph N; Kieber, Robert J; Willey, Joan D; Skrabal, Stephen A; Felix, J David; Mullaugh, Katherine M; Helms, John R

    2016-02-01

    This study reports the first ethanol concentrations in fresh and estuarine waters and greatly expands the current data set for coastal ocean waters. Concentrations for 153 individual measurements of 11 freshwater sites ranged from 5 to 598 nM. Concentrations obtained for one estuarine transect ranged from 56 to 77 nM and levels in five coastal ocean depth profiles ranged from 81 to 334 nM. Variability in ethanol concentrations was high and appears to be driven primarily by photochemical and biological processes. 47 gas phase concentrations of ethanol were also obtained during this study to determine the surface water degree of saturation with respect to the atmosphere. Generally fresh and estuarine waters were undersaturated indicating they are not a source and may be a net sink for atmospheric ethanol in this region. Aqueous phase ethanol is likely converted rapidly to acetaldehyde in these aquatic ecosystems creating the undersaturated conditions resulting in this previously unrecognized sink for atmospheric ethanol. Coastal ocean waters may act as either a sink or source of atmospheric ethanol depending on the partial pressure of ethanol in the overlying air mass. Results from this study are significant because they suggest that surface waters may act as an important vector for the uptake of ethanol emitted into the atmosphere including ethanol from biofuel production and usage.

  16. Fundamental limits on gas-phase chemical reduction of NOx in a plasma

    Energy Technology Data Exchange (ETDEWEB)

    Penetrante, B.M.; Hsiao, M.C.; Merritt, B.T.; Vogtlin, G.E. [Lawrence Livermore National Lab., CA (United States)

    1997-12-31

    In the plasma, the electrons do not react directly with the NOx molecules. The electrons collide mainly with the background gas molecules like N{sub 2}, O{sub 2} and H{sub 2}O. Electron impact on these molecules result partly in dissociation reactions that produce reactive species like N, O and OH. The NOx in the engine exhaust gas initially consist mostly of NO. The ground state nitrogen atom, N, is the only species that could lead to the chemical reduction of NO to N{sub 2}. The O radical oxidizes NO to NO{sub 2} leaving the same amount of NOx. The OH radical converts NO{sub 2} to nitric acid. Acid products in the plasma can easily get adsorbed on surfaces in the plasma reactor and in the pipes. When undetected, the absence of these oxidation products can often be mistaken for chemical reduction of NOx. In this paper the authors will examine the gas-phase chemical reduction of NOx. They will show that under the best conditions, the plasma can chemically reduce 1.6 grams of NOx per brake-horsepower-hour [g(NOx)/bhp-hr] when 5% of the engine output energy is delivered to the plasma.

  17. On the radial profile of gas-phase Fe/{\\alpha} ratio around distant galaxies

    CERN Document Server

    Zahedy, Fakhri S; Gauthier, Jean-René; Rauch, Michael

    2016-01-01

    This paper presents a study of the chemical compositions in cool gas around a sample of 27 intermediate-redshift galaxies. The sample comprises 13 massive quiescent galaxies at z=0.40-0.73 probed by QSO sightlines at projected distances d=3-400 kpc, and 14 star-forming galaxies at z=0.10-1.24 probed by QSO sightlines at d=8-163 kpc. The main goal of this study is to examine the radial profiles of the gas-phase Fe/{\\alpha} ratio in galaxy halos based on the observed Fe II to Mg II column density ratios. Because Mg+ and Fe+ share similar ionization potentials, the relative ionization correction is small in moderately ionized gas and the observed ionic abundance ratio N(Fe II)/N(Mg II) places a lower limit to the underlying (Fe/Mg) elemental abundance ratio. For quiescent galaxies, a median and dispersion of log =-0.06+/-0.15 is found at d ~100 kpc. On the other hand, star-forming galaxies exhibit log =-0.25+/-0.21 at d =-0.9+/-0.4 at larger distances. Including possible differential dust depletion or ionizati...

  18. An optical spectrum of a large isolated gas-phase PAH cation: C78H26+

    CERN Document Server

    Zhen, Junfeng; Bonnamy, Anthony; Joblin, Christine

    2015-01-01

    A gas-phase optical spectrum of a large polycyclic aromatic hydrocarbon (PAH) cation - C78H26 +- in the 410-610 nm range is presented. This large all-benzenoid PAH should be large enough to be stable with respect to photodissociation in the harsh conditions prevailing in the interstellar medium (ISM). The spectrum is obtained via multi-photon dissociation (MPD) spectroscopy of cationic C78H26 stored in the Fourier Transform Ion Cyclotron Resonance (FT-ICR) cell using the radiation from a mid-band optical parametric oscillator (OPO) laser. The experimental spectrum shows two main absorption peaks at 431 nm and 516 nm, in good agreement with a theoretical spectrum computed via time-dependent density functional theory (TD-DFT). DFT calculations indicate that the equilibrium geometry, with the absolute minimum energy, is of lowered, nonplanar C2 symmetry instead of the more symmetric planar D2h symmetry that is usually the minimum for similar PAHs of smaller size. This kind of slightly broken symmetry could produ...

  19. The general mechanisms of Cu cluster formation in the processes of condensation from the gas phase

    Indian Academy of Sciences (India)

    I V Chepkasov; Yu Ya Gafner; S L Gafner; S P Bardakhanov

    2015-06-01

    Technological applications of metallic clusters impose very strict requirements for particle size, shape, structure and defect density. Such geometrical characteristics of nanoparticles are mainly determined by the process of their growth. This work represents the basic mechanisms of cluster formation from the gas phase that has been studied on the example of copper. The process of Cu nanoclusters synthesis has been studied by the moleculardynamics method based on tight-binding potentials. It has been shown that depending on the size and temperature of the initial nanoclusters the process of nanoparticle formation can pass through different basic scenarios. The general conditions of different types of particles formation have been defined and clear dependence of the cluster shape from collision temperature of initial conglomerates has been shown. The simulation results demonstrate a very good agreement with the available experimental data. Thus, it has been shown that depending on the specific application of the synthesized particles or in electronics, where particles of a small size with a spherical shape are required, or in catalytic reactions, where the main factor of effectiveness is the maximum surface area with the help of temperature of the system it is possible to get the realization of a certain frequency of this or that scenario of the shape formation of nanocrystalline particles.

  20. Isoprene gas phase hydrogenation catalyzed by ThNi{sub 2} and UNi{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Branco, Joaquim Badalo [Departamento de Quimica, Instituto Tecnologico e Nuclear, Estrada Nacional 10, P-2686-953 Sacavem Codex (Portugal)], E-mail: jbranco@itn.pt; Goncalves, Antonio Pereira; Pires de Mato, Antonio [Departamento de Quimica, Instituto Tecnologico e Nuclear, Estrada Nacional 10, P-2686-953 Sacavem Codex (Portugal)

    2008-10-06

    The study of isoprene (2-methyl-1,3-butadiene) gas phase hydrogenation on ThNi{sub 2} and UNi{sub 2} was undertaken and the effect of the 5f element on nickel catalytic behavior investigated. At nearly steady state, the reaction products were isopentane and isopentenes (2-methyl-2-butene, 2-methyl-1-butene and 3-methyl-1-butene). The total selectivity to isopentenes was higher on ThNi{sub 2} ({approx}80 mol%) than on UNi{sub 2} ({approx}50 mol%) but, in both cases lower than that on pure Ni ({approx}96 mol%). The sum of 2-methyl-2-butene + 2-methyl-1-butene selectivities (valuable products for the tert-amyl methyl ether process) was {approx}75 mol% on ThNi{sub 2}, whereas on UNi{sub 2} it was significantly lower ({approx}50 mol%). ThNi{sub 2} and UNi{sub 2} total selectivity to isopentenes is nearly time invariant. The difference of catalytic properties between ThNi{sub 2} and UNi{sub 2} can be explained by electronic transfer from the 5f element to Ni that generates an electronic density supply on nickel, which is higher on ThNi{sub 2}.

  1. Fixed-charge phosphine ligands to explore gas-phase coinage metal-mediated decarboxylation reactions.

    Science.gov (United States)

    Vikse, Krista; Khairallah, George N; McIndoe, J Scott; O'Hair, Richard A J

    2013-05-14

    A combination of multistage mass spectrometry experiments and density functional theory (DFT) calculations were used to examine the decarboxylation reactions of a series of metal carboxylate complexes bearing a fixed-charge phosphine ligand, [(O3SC6H4)(C6H5)2PM(I)O2CR](-) (M = Cu, Ag, Au; R = Me, Et, benzyl, Ph). Collision-induced dissociation (CID) of these complexes using an LTQ linear ion mass spectrometer results in three main classes of reactions being observed: (1) decarboxylation; (2) loss of the phosphine ligand; (3) loss of carboxylic acid. The gas-phase unimolecular chemistry of the resultant decarboxylated organometallic ions, [(O3SC6H4)(C6H5)2PM(I)R](-), were also explored using CID experiments, and fragment primarily via loss of the phosphine ligand. Energy-resolved CID experiments on [(O3SC6H4)(C6H5)2PM(I)O2CR](-) (M = Cu, Ag, Au; R = Me, Et, benzyl, Ph) using a Q-TOF mass spectrometer were performed to gain a more detailed understanding of the factors influencing coinage metal-catalyzed decarboxylation and DFT calculations on the major fragmentation pathways aided in interpretation of the experimental results. Key findings are that: (1) the energy required for loss of the phosphine ligand follows the order Ag phosphine ligand on decarboxylation is also considered in comparison with previous studies on metal carboxylates that do not contain a phosphine ligand.

  2. Gas Phase Pressure Effects on the Apparent Thermal Conductivity of JSC-1A Lunar Regolith Simulant

    Science.gov (United States)

    Yuan, Zeng-Guang; Kleinhenz, Julie E.

    2011-01-01

    Gas phase pressure effects on the apparent thermal conductivity of a JSC-1A/air mixture have been experimentally investigated under steady state thermal conditions from 10 kPa to 100 kPa. The result showed that apparent thermal conductivity of the JSC-1A/air mixture decreased when pressure was lowered to 80 kPa. At 10 kPa, the conductivity decreased to 0.145 W/m/degree C, which is significantly lower than 0.196 W/m/degree C at 100 kPa. This finding is consistent with the results of previous researchers. The reduction of the apparent thermal conductivity at low pressures is ascribed to the Knudsen effect. Since the characteristic length of the void space in bulk JSC-1A varies over a wide range, both the Knudsen regime and continuum regime can coexist in the pore space. The volume ratio of the two regimes varies with pressure. Thus, as gas pressure decreases, the gas volume controlled by Knudsen regime increases. Under Knudsen regime the resistance to the heat flow is higher than that in the continuum regime, resulting in the observed pressure dependency of the apparent thermal conductivity.

  3. Isomers and conformational barriers of gas phase nicotine, nornicotine and their protonated forms

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, Tomoki; Farone, William A.; Xantheas, Sotiris S.

    2014-07-17

    We report extensive conformational searches of the neutral nicotine, nornicotine and their protonated analogs that are based on ab-initio second order Møller-Plesset perturbation (MP2) electronic structure calculations. Initial searches were performed with the 6-31G(d,p) and the energetics of the most important structures were further refined from geometry optimizations with the aug-cc-pVTZ basis set. Based on the calculated free energies at T=298 K for the gas phase molecules, neutral nicotine has two dominant trans conformers, whereas neutral nornicotine is a mixture of several conformers. For nicotine, the protonation on both the pyridine and the pyrrolidine sites is energetically competitive, whereas nornicotine prefers protonation on the pyridine nitrogen. The protonated form of nicotine is mainly a mixture of two pyridine-protonated trans conformers and two pyrrolidine-protonated trans conformers, whereas the protonated form of nornicotine is a mixture of four pyridine-protonated trans conformers. Nornicotine is conformationally more flexible than nicotine, however it is less protonated at the biologically important pyrrolidine nitrogen site. The lowest energy isomers for each case were found to interconvert via low (< 6 kcal/mol) rotational barriers around the pyridine-pyrrolidine bond.

  4. Application of a sorbent trap system to gas-phase elemental and oxidized mercury analysis.

    Science.gov (United States)

    Zhang, Zishuo; Eom, Yujin; Lee, Michelle J; Lee, Tai Gyu

    2016-07-01

    A sorbent trap that utilizes activated carbon (AC) as the solid trapping medium is a new technology for measuring total mercury (Hg) emissions from combustion facilities. In this study, sorbent trap technology was further developed, improved and evaluated at the laboratory scale. AC was impregnated with 5% aqua regia to enhance its Hg adsorption capacity. Sorbent traps spiked with an Hg standard solution were found to be reproducibly prepared and highly stable. The effect of the Hg concentration on the spiking efficiency was further investigated. The adsorption of elemental and oxidized Hg by the sorbent trap was studied under various experimental conditions (temperature, flow rate and inlet Hg concentration). The Hg concentration of the flue gas effluent from the sorbent trap was measured. In addition, the concentration of Hg adsorbed on the AC was determined by digesting the used AC with an acid according to US EPA method 3052 and then analyzing it with cold vapor atomic absorption spectrometry. Furthermore, the gas-phase Hg emissions from a combustion source were measured using the sorbent trap according to US EPA method 30B. The results showed that the sorbent trap could be used for Hg concentrations between 10.0 and 40.0 μg m(-3) and flow rates between 0.5 and 1.0 lpm with adsorption efficiencies greater than 90%.

  5. Elementary Reactions and Their Role in Gas-Phase Prebiotic Chemistry

    Directory of Open Access Journals (Sweden)

    Nadia Balucani

    2009-05-01

    Full Text Available The formation of complex organic molecules in a reactor filled with gaseous mixtures possibly reproducing the primitive terrestrial atmosphere and ocean demonstrated more than 50 years ago that inorganic synthesis of prebiotic molecules is possible, provided that some form of energy is provided to the system. After that groundbreaking experiment, gas-phase prebiotic molecules have been observed in a wide variety of extraterrestrial objects (including interstellar clouds, comets and planetary atmospheres where the physical conditions vary widely. A thorough characterization of the chemical evolution of those objects relies on a multi-disciplinary approach: 1 observations allow us to identify the molecules and their number densities as they are nowadays; 2 the chemistry which lies behind their formation starting from atoms and simple molecules is accounted for by complex reaction networks; 3 for a realistic modeling of such networks, a number of experimental parameters are needed and, therefore, the relevant molecular processes should be fully characterized in laboratory experiments. A survey of the available literature reveals, however, that much information is still lacking if it is true that only a small percentage of the elementary reactions considered in the models have been characterized in laboratory experiments. New experimental approaches to characterize the relevant elementary reactions in laboratory are presented and the implications of the results are discussed.

  6. Internal mixing of the organic aerosol by gas phase diffusion of semivolatile organic compounds

    Directory of Open Access Journals (Sweden)

    C. Marcolli

    2004-01-01

    Full Text Available This paper shows that most of the so far identified constituents of the tropospheric organic particulate matter belong to a semivolatile fraction for which gas phase diffusion in the lower troposphere is sufficiently fast to establish thermodynamic equilibrium between aerosol particles. For the first time analytical expressions for this process are derived. Inspection of vapor pressure data of a series of organic substances allows a rough estimate for which substances this mixing process must be considered. As general benchmarks we conclude that for typical aerosol radii between 0.1 and 1 µm this mixing process is efficient at 25°C for polar species with molecular weights up to 200 and for non-polar species up to 320. At −10°C, these values are shifted to 150 for polar and to 270 for non-polar substances. The extent of mixing of this semivolatile fraction is governed by equilibrium thermodynamics, leading to a selectively, though not completely, internally mixed aerosol. The internal mixing leads to a systematic depression of melting and deliquescence points of organic and mixed organic/inorganic aerosols, thus leading to an aerosol population in the lower troposphere which is predominantly liquid.

  7. Influence of salt bridge interactions on the gas-phase stability of DNA/peptide complexes

    Science.gov (United States)

    Alves, Sandra; Woods, Amina; Delvolvé, Alice; Tabet, Jean Claude

    2008-12-01

    Negative ion mode electrospray ionization mass spectrometry was used to study DNA duplexes-peptide interaction. In the present study, we show that peptides that contain two adjacent basic residues interact noncovalently with DNA single strand or duplex. Fragmentation of the complexes between peptides containing basic residues and DNA were studied under collisions and showed unexpected dissociation pathways, as previously reported for peptide-peptide interactions. The binary complexes are dissociated either along fragmentation of the covalent bonds of the peptide backbone and/or along the single DNA strand backbone cleavage without disruption of noncovalent interaction, which demonstrates the strong binding of peptide to the DNA strand. Sequential MS/MS and MSn were further performed on ternary complexes formed between duplexes and peptides to investigate the nature of interaction. The CID spectra showed as major pathway the disruption of the noncovalent interactions and the formation of binary complexes and single-strand ions, directed by the nucleic acid gas-phase acidity. Indeed, a preferential formation of complexes with thymidine containing single strands is observed. An alternative pathway is also detected, in which complexes are dissociated along the covalent bond of the peptide and/or DNA according to the basicity. Our experimental data suggest the presence of strong salt bridge interactions between DNA and peptides containing basic residues.

  8. Gas Phase Rovibrational Spectroscopy of Dmso, Part II: Towards the Terahertz Observation of 4-FOLD Clusters

    Science.gov (United States)

    Cuisset, Arnaud; Martin-Drumel, Marie-Aline; Hindle, Francis; Mouret, Gael; Sadovskii, Dmitrii A.

    2013-06-01

    Benefiting of the exceptional properties of the AILES synchrotron beamline, the gas phase Far-IR spectrum of DMSO has been recorded and resolved. The rovibrational analysis allowed to discover a new rotational behaviour for a polyatomic molecule: the gyroscopic destabilization. In order to explain this phenomenon, we looked for four-fold energy clusters in the high resolution ground state THz spectrum of DMSO recorded with a sub-THz spectrometer based on a frequency multiplication chain. Pure rotational lines in the 5 lowest vibrationnally excited levels have been recorded below 700 GHz. With near 1000 rotational transitions assigned, high quantum numbers have been reached allowing to discover sequence of four-fold clusters in the out of plane bending mode of DMSO and to study the vibrational dependence of an unusual rotational dynamics. J. B. Brubach et al., AIP Conf. Proc., 1214, (81), 2010. A. Cuisset, L. Nanobashvili, I. Smirnova, R. Bocquet, F. Hindle, G. Mouret, O. Pirali, P. Roy, D. Sadovskii,Chem. Phys. Lett., 492,(30),2010 A. Cuisset, O. Pirali, D. Sadovskii,Phys. Rev. Lett., 109,(094101), 2012. G. Mouret, M. Guinet, A. Cuisset, L. Croizet, S. Eliet, R. Bocquet, F. Hindle, IEEE Sensors Journal, 13, 1, 2013.

  9. Evaluation of the potentials of humic acid removal in water by gas phase surface discharge plasma.

    Science.gov (United States)

    Wang, Tiecheng; Qu, Guangzhou; Ren, Jingyu; Yan, Qiuhe; Sun, Qiuhong; Liang, Dongli; Hu, Shibin

    2016-02-01

    Degradation of humic acid (HA), a predominant type of natural organic matter in ground water and surface waters, was conducted using a gas phase surface discharge plasma system. HA standard and two surface waters (Wetland, and Weihe River) were selected as the targets. The experimental results showed that about 90.9% of standard HA was smoothly removed within 40 min's discharge plasma treatment at discharge voltage 23.0 kV, and the removal process fitted the first-order kinetic model. Roles of some active species in HA removal were studied by evaluating the effects of solution pH and OH radical scavenger; and the results presented that O3 and OH radical played significant roles in HA removal. Scanning electron microscope (SEM) and FTIR analysis showed that HA surface topography and molecular structure were changed during discharge plasma process. The mineralization of HA was analyzed by UV-Vis spectrum, dissolved organic carbon (DOC), specific UV absorbance (SUVA), UV absorption ratios, and excitation-emission matrix (EEM) fluorescence. The formation of disinfection by-products during HA sample chlorination was also identified, and CHCl3 was detected as the main disinfection by-product, but discharge plasma treatment could suppress its formation to a certain extent. In addition, approximately 82.3% and 67.9% of UV254 were removed for the Weihe River water and the Wetland water after 40 min of discharge plasma treatment.

  10. Photoisomerization action spectrum of retinal protonated Schiff base in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Coughlan, N. J. A.; Catani, K. J.; Adamson, B. D.; Wille, U.; Bieske, E. J., E-mail: evanjb@unimelb.edu.au [School of Chemistry, The University of Melbourne, Victoria 3010 (Australia)

    2014-04-28

    The photophysical behaviour of the isolated retinal protonated n-butylamine Schiff base (RPSB) is investigated in the gas phase using a combination of ion mobility spectrometry and laser spectroscopy. The RPSB cations are introduced by electrospray ionisation into an ion mobility mass spectrometer where they are exposed to tunable laser radiation in the region of the S{sub 1} ← S{sub 0} transition (420–680 nm range). Four peaks are observed in the arrival time distribution of the RPSB ions. On the basis of predicted collision cross sections with nitrogen gas, the dominant peak is assigned to the all-trans isomer, whereas the subsidiary peaks are assigned to various single, double and triple cis geometric isomers. RPSB ions that absorb laser radiation undergo photoisomerization, leading to a detectable change in their drift speed. By monitoring the photoisomer signal as a function of laser wavelength an action spectrum, extending from 480 to 660 nm with a clear peak at 615 ± 5 nm, is obtained. The photoisomerization action spectrum is related to the absorption spectrum of isolated retinal RPSB molecules and should help benchmark future electronic structure calculations.

  11. Soft X-ray photoemission spectroscopy of selected neurotransmitters in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Maris, Assimo; Melandri, Sonia; Evangelisti, Luca; Caminati, Walther [Dipartimento di Chimica ' G. Ciamician' dell' Universita, Via Selmi 2, I-40126 Bologna (Italy); Giuliano, Barbara M. [Departamento de Quimica da Universidade de Coimbra, 3004-535 Coimbra (Portugal); Plekan, Oksana [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); Feyer, Vitaliy [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); Electronic Properties (PGI-6), Peter Gruenberg Institute, Forschungszentrum Juelich GmbH, Leo-Brandt-Strasse, 52428 Juelich (Germany); Richter, Robert [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); Coreno, Marcello [CNR-IMIP, Montelibretti, I-00016 Rome (Italy); Prince, Kevin C., E-mail: kevin.prince@elettra.trieste.it [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); CNR-IOM, Laboratorio TASC, I-34149 Basovizza, Trieste (Italy)

    2012-09-15

    Highlights: Black-Right-Pointing-Pointer Neurotransmitter molecules. Black-Right-Pointing-Pointer Photoelectron spectroscopy. Black-Right-Pointing-Pointer Electronic structure. Black-Right-Pointing-Pointer Weak hydrogen bonding. -- Abstract: The valence molecular orbitals and core levels of tyramine, tryptamine and tryptophol in the gas phase have been studied using X-ray photoelectron spectroscopy (XPS) and theoretical methods. The energies of the outer valence region spectrum are found to be in agreement with previously reported He I spectra, while new data on the inner valence molecular orbitals are reported. The structures in the carbon, nitrogen and oxygen core level spectra of these molecules have been identified and assigned. These compounds are characterised by conformers with hydrogen bonding in which the {pi} systems of the phenol and indole groups act as hydrogen acceptors, but a spectroscopic signature of this hydrogen bond was not observed. This is in contrast with our previous spectra of amino acids, where conformers with specific hydrogen bonding showed strong effects in core level spectra. We attribute the difference to the weaker strength of the {pi}-hydrogen bonding.

  12. Degradation of dyes by active species injected from a gas phase surface discharge

    Science.gov (United States)

    Li, Jie; Wang, Tiecheng; Lu, Na; Zhang, Dandan; Wu, Yan; Wang, Tianwei; Sato, Masayuki

    2011-06-01

    A reactor, based on the traditional gas phase surface discharge (GPSD), is designed for degradation of dye wastewater in this study. The reactor is characterized by using the dye wastewater as a ground electrode. A spiral discharge electrode of stainless steel wire attached on the inside wall of a cylindrical insulating medium and the wastewater surrounding the insulating medium for simultaneous cooling of the discharge electrode constitute the reactor. The active chemical radicals generated by the discharge of the spiral electrode are injected into the water with the carrier gas. The removal of three organic dyes (including methyl red (MR), reactive brilliant blue (RBB) and cationic red (CR)) in aqueous solution is investigated. The effects of electrode configuration, discharge voltage and solution pH value on the decoloration efficiency of MR are discussed. The experimental results show that over 95% of decoloration efficiencies for all the dyes are obtained after several minutes of plasma treatment. 40% of chemical oxygen demand removal of MR is obtained after 8 min of discharge treatment. Furthermore, it is found that ozone mainly affects the removal of dyes and several aliphatic compounds are identified as the oxidation products of MR. The possible degradation pathways of MR by GPSD are proposed.

  13. Preparative soft and reactive landing of gas-phase ions on plasma-treated metal surfaces.

    Science.gov (United States)

    Volný, Michael; Elam, W Timothy; Ratner, Buddy D; Turecek, Frantisek

    2005-08-01

    Soft landing of singly charged gas-phase ions on dry metal surfaces that were pretreated in situ by oxygen plasma results in 0.1-2% total yields of recovered intact compounds. Lysine, peptides, crystal violet dye, and a biotin conjugate are found to survive soft landing of hyperthermal ions of up to 50-eV kinetic energy. Soft landing at 40-50-eV ion kinetic energies of a fluorescence-labeled biotin conjugate results in an immobilized fraction that cannot be washed from the surface and is found to contain an intact biotin moiety. The present results represent an approximately 10(4) fold improvement in soft-landing efficiency and indicate that plasma-treated metal surfaces can be useful for preparative separation of organic and biological molecules by mass spectrometry. The substantial improvement in soft-landing yields results from a high transmission of electrosprayed ions into the vacuum system, efficient and nondestructive discharge of ions on the metal oxide surface, and facile analyte recovery in the absence of a matrix.

  14. Photocatalytic Oxidation of Aniline in the Gas Phase Using Porous TiO2 Thin Films

    Institute of Scientific and Technical Information of China (English)

    Fa Wenjun; Li Ying; Gong Chuqing; Zhong Jiacheng

    2006-01-01

    The gas-phase photocatalytic oxidation of aniline on a new kind of porous nano-TiO2 composite films is investigated.The composite film was prepared on glass fiber with the water glass as binders and dilute H2SO4 solution as solidifying reagent.The surface characters were observed by scanning electron microscope.The photocatalytic degradation of aniline on the composite films was carried out in a TiO2AJV system.Some important factors affecting the photodegmdation,such as the concentration of TiO2,the initial concentration of aniline,and the existing water vapor,are also studied.The product ofphotocatalytic oxidation was detected by Fourier transform-Infrared.The partial intermediate products were absorbed on TiO2 surface,which resulted in catalyst deactivation.But when it was irradiated under UV illumination or solar irradiation for some time,the catalyst could be reused without loss of catalytic activity.

  15. CdSe Nanoparticles with Clean Surfaces: Gas Phase Synthesis and Optical Properties

    Directory of Open Access Journals (Sweden)

    Zhang Hongwei

    2015-01-01

    Full Text Available CdSe nanoparticles (NPs were generated in gas phase with a magnetron plasma gas aggregation cluster beam source. Coagulation-free CdSe nanocrystals with very clean particle surface and interface, as well as a fairly uniform spatial distribution were obtained. The deposited NPs have a good dispersity with a mean diameter of about 4.8nm. A strong photoluminescence band corresponding to the near- band-edge transition of the CdSe NPs was observed. The CdSe NP films show a significant photoconductance induced by laser irradiation. With an applied bias voltage of 10V, the photo- induced current can be as high as 0.4mA under 0.01mW/mm2 405nm laser illumination. Our approach offers an alternative method for CdSe NP synthesis, which has the advantages such as high purity, good process and product control, as well as mass production, as compared to the existing methods.

  16. Decomposition of gas-phase diphenylether at 473 K by electron beam generated plasma

    CERN Document Server

    Kim, H H; Kojima, T

    2003-01-01

    Decomposition of gas-phase diphenylether (DPE) in the order of several parts per million by volume (ppmv) was studied as a model compound of dioxin using a flow-type electron-beam reactor at an elevated temperature of 473 K. The ground state oxygen ( sup 3 P) atoms played an important role in the decomposition of DPE resulting in the formation of 1,4-hydroquinone (HQ) as a major ring retaining product. The high yield of hydroquinone indicated that the breakage of ether bond (C-O) is important in the initial step of DPE decomposition. Ring cleavage products were CO and CO sub 2 , and NO sub 2 was also produced from background N sub 2 -O sub 2. The sum of the yields of HQ, CO sub 2 and CO accounts for over 90% of the removed DPE. Hydroxyl radicals (OH) were less important in the dilute DPE decomposition at a high water content, and were mostly consumed by recombination reactions to form hydrogen peroxide. The smaller the initial DPE concentrations, the higher the decomposition efficiency and the lower the yield...

  17. Laboratory investigations of the alpha-pinene/ozone gas-phase reaction

    Energy Technology Data Exchange (ETDEWEB)

    Benner, C.L.

    1985-01-01

    In order to provide more insight into terpene photooxidation or ozonolysis reaction mechanisms, a radiotracer technique was developed. This technique was applied to an investigation of the /sup 14/C-alpha-pinene/ozone reaction. In the first phase of the research, the carbon distribution at the conclusion of the ozonolysis reaction was determined by separating carbon-14-labelled gaseous products from labelled aerosols, and counting each phase by liquid scintillation methods. The resulting carbon balance was 38% to 60% filtered aerosols, 6% to 20% gas phase compounds, and 11% to 29% products absorbed on the reaction chamber walls. Recoveries of the alpha-pinene carbon-14 ranging from 79% to 97% were achieved using this method. The alpha-pinene concentrations in these experiments were close to ambient (1 part per billion), yet the carbon balance was similar to that observed at much higher concentrations (>1 part per million). In the second phase of the alpha-pinene study, both gas and aerosol products of the ozonolysis reaction were collected on cartridges impregnated with 2,4-dinitrophenylhydrazine, then analyzed by HPLC. In the final experiments, alpha-pinene aerosol was reacted with a silylating agent to improve the detection of organic acids and alcohols. The gas chromatographic/mass spectrometric analysis of the silylated aerosol products showed evidence of dimer/polymer formation occurring in the ozonolysis reaction.

  18. Dynamics and Predictive Control of Gas Phase Propylene Polymerization in Fluidized Bed Reactors

    Institute of Scientific and Technical Information of China (English)

    Ahmad Shamiri; Mohamed azlan Hussain; Farouq sabri Mjalli; Navid Mostoufi; Seyedahmad Hajimolana

    2013-01-01

    A two-phase dynamic model, describing gas phase propylene polymerization in a fluidized bed reactor, was used to explore the dynamic behavior and process control of the polypropylene production rate and reactor temperature. The open loop analysis revealed the nonlinear behavior of the polypropylene fluidized bed reactor, jus-tifying the use of an advanced control algorithm for efficient control of the process variables. In this case, a central-ized model predictive control (MPC) technique was implemented to control the polypropylene production rate and reactor temperature by manipulating the catalyst feed rate and cooling water flow rate respectively. The corre-sponding MPC controller was able to track changes in the setpoint smoothly for the reactor temperature and pro-duction rate while the setpoint tracking of the conventional proportional-integral (PI) controller was oscillatory with overshoots and obvious interaction between the reactor temperature and production rate loops. The MPC was able to produce controller moves which not only were well within the specified input constraints for both control vari-ables, but also non-aggressive and sufficiently smooth for practical implementations. Furthermore, the closed loop dynamic simulations indicated that the speed of rejecting the process disturbances for the MPC controller were also acceptable for both controlled variables.

  19. Diffusion in the gas phase: the effects of ambient pressure and gas composition.

    Science.gov (United States)

    Paganelli, C V; Rahn, A A; Wangensteen, O D

    1975-12-01

    Gas transport across the pores of a hen's egg shell occurs by a process of diffusion in the gas phase and for any particular gas depends upon its diffusion coefficient and the pore geometry. The egg shell is thus a convenient model for measuring the diffusive permeability of the shell to a given gas species when its diffusion coefficient is altered by either a change in ambient pressure or by changing the second gas in the diffusion pathway. In this study the permeability of the shell to water vapor and O2 was inversely proportional to ambient pressures over the range of .06 to 8 atmospheres' absolute (ata). The permeability of the shell to water vapor in a He environment (KH20, He) was 2.4 times KH20, air. If KO2, N2 is taken as unity, the permeabilities of the shell to O2 in He, Ar, CO2 and SF6 are 3.38, 0.95, 0.88, and 0.52, respectively. The results are interpreted in terms of the Chapman-Enskog equation, from which binary diffusion coefficients can be predicted for given gas pairs and ambient pressures. These results also provide explantations for the structural modification of egg shells in altitude-adapted chickens, and for the reduced insensible water loss in man at high ambient pressure.

  20. The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase

    Science.gov (United States)

    Haas, George W.; Giblin, Daryl E.; Gross, Michael L.

    1998-01-01

    In solution, base-catalyzed hydrolysis and transesterification of esters are initiated by hydroxide- or alkoxide-ion attack at the carbonyl carbon. At low pressures in the gas phase, however, transesterification proceeds by an attack of the enolate anion of an acetate ester on an alcohol. Fourier transform mass spectrometry (FTMS) indicates that the reaction is the second-order process: -CH2-CO2-R + R'-OH --> - CH2-CO2-R' + R-OH and there is little to no detectable production of either alkoxide anion. Labeling studies show that the product and reactant enolate anion esters undergo exchange of hydrogens located [alpha] to the carbonyl carbon with the deuterium of R'-OD. The extent of the H/D exchange increases with reaction time, pointing to a short-lived intermediate. The alcoholysis reaction rate constants increase with increasing acidity of the primary, straight-chained alkyl alcohols, whereas steric effects associated with branched alcohols cause the rate constants to decrease. Equilibrium constants, which were determined directly from measurements at equilibrium and which were calculated from the forward and reverse rate constants, are near unity and show internal consistency. In the absence of steric effects, the larger enolate is always the favored product at equilibrium. The intermediate for the transesterification reaction, which can be generated at a few tenths of a torr in a tandem mass spectrometer, is tetrahedral, but other adducts that are collisionally stabilized under these conditions are principally loosely bound complexes.

  1. The reaction of CF2Cl2 with gas-phase hydrated electrons.

    Science.gov (United States)

    Lengyel, Jozef; van der Linde, Christian; Fárník, Michal; Beyer, Martin K

    2016-09-14

    The reaction of dichlorodifluoromethane (CF2Cl2) with hydrated electrons (H2O)n(-) (n = 30-86) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The hydrated electron reacts with CF2Cl2, forming (H2O)mCl(-) with a rate constant of (8.6 ± 2.2) × 10(-10) cm(3) s(-1), corresponding to an efficiency of 57 ± 15%. The reaction enthalpy was determined using nanocalorimetry, revealing a strongly exothermic reaction with ΔHr(CF2Cl2, 298 K) = -208 ± 41 kJ mol(-1). The combination of the measured reaction enthalpy with thermochemical data from the condensed phase yields a C-Cl bond dissociation enthalpy (BDE) ΔHC-Cl(CF2Cl2, 298 K) = 355 ± 41 kJ mol(-1) that agrees within error limits with the predicted values from quantum chemical calculations and published BDEs.

  2. First detection of gas-phase methanol in a protoplanetary disk

    CERN Document Server

    Walsh, Catherine; Oberg, Karin I; Kama, Mihkel; Hoff, Merel L R van 't; Millar, Tom J; Aikawa, Yuri; Herbst, Eric; Weaver, Susanna L Widicus; Nomura, Hideko

    2016-01-01

    The first detection of gas-phase methanol in a protoplanetary disk (TW Hya) is presented. In addition to being one of the largest molecules detected in disks to date, methanol is also the first disk organic molecule with an unambiguous ice chemistry origin. The stacked methanol emission, as observed with ALMA, is spectrally resolved and detected across six velocity channels ($>3 \\sigma$), reaching a peak signal-to-noise of $5.5\\sigma$, with the kinematic pattern expected for TW~Hya. Using an appropriate disk model, a fractional abundance of $3\\times 10^{-12} - 4 \\times 10^{-11}$ (with respect to H$_2$) reproduces the stacked line profile and channel maps, with the favoured abundance dependent upon the assumed vertical location (midplane versus molecular layer). The peak emission is offset from the source position suggesting that the methanol emission has a ring-like morphology: the analysis here suggests it peaks at $\\approx 30$~AU reaching a column density $\\approx 3-6\\times10^{12}$~cm$^{-2}$. In the case of...

  3. Graphical Interface for the Study of Gas-Phase Reaction Kinetics: Cyclopentene Vapor Pyrolysis

    Science.gov (United States)

    Marcotte, Ronald E.; Wilson, Lenore D.

    2001-06-01

    The undergraduate laboratory experiment on the pyrolysis of gaseous cyclopentene has been modernized to improve safety, speed, and precision and to better reflect the current practice of physical chemistry. It now utilizes virtual instrument techniques to create a graphical computer interface for the collection and display of experimental data. An electronic pressure gauge has replaced the mercury manometer formerly needed in proximity to the 500 °C pyrolysis oven. Students have much better real-time information available to them and no longer require multiple lab periods to get rate constants and acceptable Arrhenius parameters. The time saved on manual data collection is used to give the students a tour of the computer interfacing hardware and software and a hands-on introduction to gas-phase reagent preparation using a research-grade high-vacuum system. This includes loading the sample, degassing it by the freeze-pump-thaw technique, handling liquid nitrogen and working through the logic necessary for each reconfiguration of the diffusion pump section and the submanifolds.

  4. The origin of gas-phase HCO and CH3O radicals in prestellar cores

    CERN Document Server

    Bacmann, Aurore

    2016-01-01

    The recent unexpected detection of terrestrial complex organic molecules in the cold (~ 10 K) gas has cast doubts on the commonly accepted formation mechanisms of these species. Standard gas-phase mechanisms are inefficient and tend to underproduce these molecules, and many of the key reactions involved are unconstrained. Grain-surface mechanisms, which were presented as a viable alternative, suffer from the fact that they rely on grain surface diffusion of heavy radicals, which is not possible thermally at very low temperatures. One of the simplest terrestrial complex organic molecules, methanol is believed to form on cold grain surfaces following from successive H atom additions on CO. Unlike heavier species, H atoms are very mobile on grain surfaces even at 10 K. Intermediate species involved in grain surface methanol formation by CO hydrogenation are the radicals HCO and CH3O, as well as the stable species formaldehyde H2CO. These radicals are thought to be precursors of complex organic molecules on grain...

  5. Removal of pyridine from liquid and gas phase by copper forms of natural and synthetic zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Rehakova, Maria, E-mail: maria.rehakova@upjs.sk [Institute of Chemistry, Faculty of Science, P.J. Safarik University, 041 54 Kosice (Slovakia); Fortunova, Lubica [Institute of Chemistry, Faculty of Science, P.J. Safarik University, 041 54 Kosice (Slovakia); Bastl, Zdenek [J. Heyrovsky Institute of Physical Chemistry, ASCR, v.v.i., 18223 Prague 8 (Czech Republic); Nagyova, Stanislava [Department of Physics, Electrotechnical Faculty, Technical University, 042 00 Kosice (Slovakia); Dolinska, Silvia [Institute of Geotechnics, Slovak Academy of Sciences, 043 53 Kosice (Slovakia); Jorik, Vladimir [Department of Inorganic Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, 81237 Bratislava (Slovakia); Jona, Eugen [Department of Chemistry and Technology of Inorganic Materials, Faculty of Industrial Technologies, Trencin University of Alexander Dubcek, 02032 Puchov (Slovakia)

    2011-02-15

    Zeoadsorbents on the basis of copper forms of synthetic zeolite ZSM5 and natural zeolite of the clinoptilolite type (CT) have been studied taking into account their environmental application in removing harmful pyridine (py) from liquid and gas phase. Sorption of pyridine by copper forms of zeolites (Cu-ZSM5 and Cu-CT) has been studied by CHN, X-ray photoelectron spectroscopy, X-ray powder diffractometry, FTIR spectroscopy, thermal analysis (TG, DTA and DTG) and analysis of the surface areas and the pore volumes by low-temperature adsorption of nitrogen. The results of thermal analyses of Cu-ZSM5, Cu-(py){sub x}ZSM5, Cu-CT and Cu-(py){sub x}CT zeolitic products with different composition (x depends on the experimental conditions of sorption of pyridine) clearly confirmed their different thermal properties as well as the sorption of pyridine. In the zeolitic pyridine containing samples the main part of the pyridine release process occurs at considerably higher temperatures than is the boiling point of pyridine, which proves strong bond and irreversibility of py-zeolite interaction. FTIR spectra of Cu-(py){sub x}zeolite samples showed well resolved bands of pyridine. The results of thermal analysis and FTIR spectroscopy are in a good agreement with the results of other used methods.

  6. Removal of pyridine from liquid and gas phase by copper forms of natural and synthetic zeolites.

    Science.gov (United States)

    Reháková, Mária; Fortunová, Lubica; Bastl, Zdeněk; Nagyová, Stanislava; Dolinská, Silvia; Jorík, Vladimír; Jóna, Eugen

    2011-02-15

    Zeoadsorbents on the basis of copper forms of synthetic zeolite ZSM5 and natural zeolite of the clinoptilolite type (CT) have been studied taking into account their environmental application in removing harmful pyridine (py) from liquid and gas phase. Sorption of pyridine by copper forms of zeolites (Cu-ZSM5 and Cu-CT) has been studied by CHN, X-ray photoelectron spectroscopy, X-ray powder diffractometry, FTIR spectroscopy, thermal analysis (TG, DTA and DTG) and analysis of the surface areas and the pore volumes by low-temperature adsorption of nitrogen. The results of thermal analyses of Cu-ZSM5, Cu-(py)(x)ZSM5, Cu-CT and Cu-(py)(x)CT zeolitic products with different composition (x depends on the experimental conditions of sorption of pyridine) clearly confirmed their different thermal properties as well as the sorption of pyridine. In the zeolitic pyridine containing samples the main part of the pyridine release process occurs at considerably higher temperatures than is the boiling point of pyridine, which proves strong bond and irreversibility of py-zeolite interaction. FTIR spectra of Cu-(py)(x)zeolite samples showed well resolved bands of pyridine. The results of thermal analysis and FTIR spectroscopy are in a good agreement with the results of other used methods.

  7. Formation of Carbamate Anions by the Gas-phase Reaction of Anilide Ions with CO2.

    Science.gov (United States)

    Liu, Chongming; Nishshanka, Upul; Attygalle, Athula B

    2016-05-01

    The anilide anion (m/z 92) generated directly from aniline, or indirectly as a fragmentation product of deprotonated acetanilide, captures CO2 readily to form the carbamate anion (m/z 136) in the collision cell, when CO2 is used as the collision gas in a tandem-quadrupole mass spectrometer. The gas-phase affinity of the anilide ion to CO2 is significantly higher than that of the phenoxide anion (m/z 93), which adds to CO2 only very sluggishly. Our results suggest that the efficacy of CO2 capture depends on the natural charge density on the nitrogen atom, and relative nucleophilicity of the anilide anion. Generally, conjugate bases generated from aniline derivatives with proton affinities (PA) less than 350 kcal/mol do not tend to add CO2 to form gaseous carbamate ions. For example, the anion generated from p-methoxyaniline (PA = 367 kcal/mol) reacts significantly faster than that obtained from p-nitroaniline (PA = 343 kcal/mol). Although deprotonated p-aminobenzoic acid adds very poorly because the negative charge is now located primarily on the carboxylate group, it reacts more efficiently with CO2 if the carboxyl group is esterified. Moreover, mixture of CO2 and He as the collision gas was found to afford more efficient adduct formation than CO2 alone, or as mixtures made with nitrogen or argon, because helium acts as an effective "cooling" gas and reduces the internal energy of reactant ions.

  8. Non-conventional gas phase remediation of volatile halogenated compounds by dehydrated bacteria.

    Science.gov (United States)

    Erable, Benjamin; Goubet, Isabelle; Seltana, Amira; Maugard, Thierry

    2009-06-01

    Traditional biological removal processes are limited by the low solubility of halogenated compounds in aqueous media. A new technology appears very suitable for the remediation of these volatile organic compounds (VOCs). Solid/gas bio-catalysis applied in VOC remediation can transform halogenated compounds directly in the gas phase using dehydrated cells as a bio-catalyst. The hydrolysis of volatile halogenated substrates into the corresponding alcohol was studied in a solid/gas biofilter where lyophilised bacterial cultures were used as the catalyst. Four strains containing dehalogenase enzymes were tested for the hydrolysis of 1-chlorobutane. The highest removal yield was obtained using the dhaA-containing strains, the maximal reaction rate of 0.8 micromol min(-1)g(-1) being observed with Escherichia coli BL21(DE3)(dhaA). Various treatments such as cell disruption by lysozyme or alkaline gas addition in the bio-filter could stabilise the dehalogenase activity of the bacteria. A pre-treatment of the dehydrated bacterial cells by ammonia vapour improved the stability of the catalyst and a removal activity of 0.9 micromol min(-1)g(-1) was then obtained for 60h. Finally, the process was extended to a range of halogenated substrates including bromo- and chloro-substrates. It was shown that the removal capacity for long halogenated compounds (C(5)-C(6)) was greatly increased relative to traditional biological processes.

  9. Gas phase dispersion in compost as a function of different water contents and air flow rates

    Science.gov (United States)

    Sharma, Prabhakar; Poulsen, Tjalfe G.

    2009-07-01

    Gas phase dispersion in a natural porous medium (yard waste compost) was investigated as a function of gas flow velocity and compost volumetric water content using oxygen and nitrogen as tracer gases. The compost was chosen because it has a very wide water content range and because it represents a wide range of porous media, including soils and biofilter media. Column breakthrough curves for oxygen and nitrogen were measured at relatively low pore gas velocities, corresponding to those observed in for instance soil vapor extraction systems or biofilters for air cleaning at biogas plants or composting facilities. Total gas mechanical dispersion-molecular diffusion coefficients were fitted from the breakthrough curves using a one-dimensional numerical solution to the advection-dispersion equation and used to determine gas dispersivities at different volumetric gas contents. The results showed that gas mechanical dispersion dominated over molecular diffusion with mechanical dispersion for all water contents and pore gas velocities investigated. Importance of mechanical dispersion increased with increasing pore gas velocity and compost water content. The results further showed that gas dispersivity was relatively constant at high values of compost gas-filled porosity but increased with decreasing gas-filled porosity at lower values of gas-filled porosity. Results finally showed that measurement uncertainty in gas dispersivity is generally highest at low values of pore gas velocity.

  10. Evaluation of Chemical Interactions between Small Molecules in the Gas Phase Using Chemical Force Microscopy.

    Science.gov (United States)

    Lee, Jieun; Ju, Soomi; Kim, In Tae; Jung, Sun-Hwa; Min, Sun-Joon; Kim, Chulki; Sim, Sang Jun; Kim, Sang Kyung

    2015-12-04

    Chemical force microscopy analyzes the interactions between various chemical/biochemical moieties in situ. In this work we examined force-distance curves and lateral force to measure the interaction between modified AFM tips and differently functionalized molecular monolayers. Especially for the measurements in gas phase, we investigated the effect of humidity on the analysis of force-distance curves and the images in lateral force mode. Flat chemical patterns composed of different functional groups were made through micro-contact printing and lateral force mode provided more resolved analysis of the chemical patterns. From the images of 1-octadecanethiol/11-mercapto-1-undecanoic acid patterns, the amine group functionalized tip brought out higher contrast of the patterns than an intact silicon nitride tip owing to the additional chemical interaction between carboxyl and amine groups. For more complex chemical interactions, relative chemical affinities toward specific peptides were assessed on the pattern of 1-octadecanethiol/phenyl-terminated alkanethiol. The lateral image of chemical force microscopy reflected specific preference of a peptide to phenyl group as well as the hydrophobic interaction.

  11. A Unified Representation of Gas-Phase Element Depletions in the Interstellar Medium

    CERN Document Server

    Jenkins, Edward B

    2009-01-01

    A study of gas-phase element abundances reported in the literature for 17 different elements sampled over 243 sight lines in the local part of our Galaxy reveals that the depletions into solid form (dust grains) are extremely well characterized by trends that employ only three kinds of parameters. One is an index that describes the overall level of depletion applicable to the gas in any particular sight line, and the other two represent linear coefficients that describe how to derive each element's depletion from this sight-line parameter. The information from this study reveals the relative proportions of different elements that are incorporated into dust at different stages of grain growth. An extremely simple scheme is proposed for deriving the dust contents and metallicities of absorption-line systems that are seen in the spectra of distant quasars or the optical afterglows of gamma-ray bursts. Contrary to presently accepted thinking, the elements sulfur and krypton appear to show measurable changes in th...

  12. Reactive and inelastic processes in the gas-phase at ultra-low temperatures

    CERN Document Server

    Chastaing, D

    2000-01-01

    This thesis reports the gas-phase kinetic study of reactions between neutral species of astrophysical importance, over a wide range of temperatures, from 295 K down to 15 K. Such extremely low temperatures were provided by the CRESU technique (Cinetique de Reaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow). The kinetics of the reactions of ethynyl radical (C sub 2 H) with oxygen (O sub 2) and unsaturated hydrocarbons (C sub 2 H sub 2 , C sub 2 H sub 4 , C sub 3 H sub 6) has been investigated for the first time down to such extremely low temperatures, using a laser photolysis - chemiluminescence technique. Rate coefficients of the reactions of ground state carbon atom with O sub 2 , NO, C sub 2 H sub 2 , C sub 2 H sub 4 and the two C sub 3 H sub 4 isomers (allene and methyl acetylene) have been measured, using a direct detection technique (laser induced fluorescence). These investigations are of particular interest for the improvement of theoretical models which seek ...

  13. Single-step gas phase synthesis of stable iron aluminide nanoparticles with soft magnetic properties

    Directory of Open Access Journals (Sweden)

    Jerome Vernieres

    2014-11-01

    Full Text Available Soft magnetic alloys at the nanoscale level have long generated a vivid interest as candidate materials for technological and biomedical purposes. Consequently, controlling the structure of bimetallic nanoparticles in order to optimize their magnetic properties, such as high magnetization and low coercivity, can significantly boost their potential for related applications. However, traditional synthesis methods stumble upon the long standing challenge of developing true nanoalloys with effective control over morphology and stability against oxidation. Herein, we report on a single-step approach to the gas phase synthesis of soft magnetic bimetallic iron aluminide nanoparticles, using a versatile co-sputter inert gas condensation technique. This method allowed for precise morphological control of the particles; they consisted of an alloy iron aluminide crystalline core (DO3 phase and an alumina shell, which reduced inter-particle interactions and also prevented further oxidation and segregation of the bimetallic core. Remarkably, the as-deposited alloy nanoparticles show interesting soft magnetic properties, in that they combine a high saturation magnetization (170 emu/g and low coercivity (less than 20 Oe at room temperature. Additional functionality is tenable by modifying the surface of the particles with a polymer, to ensure their good colloidal dispersion in aqueous environments.

  14. High-Pressure Acceleration of Nanoliter Droplets in the Gas Phase in a Microchannel

    Directory of Open Access Journals (Sweden)

    Yutaka Kazoe

    2016-08-01

    Full Text Available Microfluidics has been used to perform various chemical operations for pL–nL volumes of samples, such as mixing, reaction and separation, by exploiting diffusion, viscous forces, and surface tension, which are dominant in spaces with dimensions on the micrometer scale. To further develop this field, we previously developed a novel microfluidic device, termed a microdroplet collider, which exploits spatially and temporally localized kinetic energy. This device accelerates a microdroplet in the gas phase along a microchannel until it collides with a target. We demonstrated 6000-fold faster mixing compared to mixing by diffusion; however, the droplet acceleration was not optimized, because the experiments were conducted for only one droplet size and at pressures in the 10–100 kPa range. In this study, we investigated the acceleration of a microdroplet using a high-pressure (MPa control system, in order to achieve higher acceleration and kinetic energy. The motion of the nL droplet was observed using a high-speed complementary metal oxide semiconductor (CMOS camera. A maximum droplet velocity of ~5 m/s was achieved at a pressure of 1–2 MPa. Despite the higher fluid resistance, longer droplets yielded higher acceleration and kinetic energy, because droplet splitting was a determining factor in the acceleration and using a longer droplet helped prevent it. The results provide design guidelines for achieving higher kinetic energies in the microdroplet collider for various microfluidic applications.

  15. Fingerprint vibrational spectra of protonated methyl esters of amino acids in the gas phase.

    Science.gov (United States)

    Simon, Aude; Macaleese, Luke; Maître, Philippe; Lemaire, Joël; McMahon, Terrance B

    2007-03-14

    Infrared spectra of the protonated monomers of glycine, alanine, valine, and leucine methyl esters are presented. These protonated species are generated in the gas phase via matrix assisted laser desorption ionization (MALDI) within the cell of a Fourier transform ion cyclotron resonance spectrometer (FTICR) where they are subsequently mass selected as the only species trapped in the FTICR cell. Alternatively, they have also been generated by electrospray ionization and transferred to a Paul ion-trap mass spectrometer where they are similarly isolated. In both cases IR spectra are then derived from the frequency dependence of the infrared multiple photon dissociation (IRMPD) in the mid-infrared region (1000-2200 cm(-1)), using the free electron laser facility Centre de Laser Infrarouge d'Orsay (CLIO). IR bands are assigned by comparison with the calculated vibrational spectra of the lowest energy isomers using density functional theory (DFT) calculations. There is in general good agreement between experimental IRMPD spectra and calculated IR absorption spectra for the lowest energy conformer which provides evidence for conformational preferences. The two different approaches to ion generation and trapping yield IRMPD spectra that are in excellent agreement.

  16. NMR properties of hydrogen-bonded glycine cluster in gas phase

    Science.gov (United States)

    Carvalho, Jorge R.; da Silva, Arnaldo Machado; Ghosh, Angsula; Chaudhuri, Puspitapallab

    2016-11-01

    Density Functional Theory (DFT) calculations have been performed to study the effect of the hydrogen bond formation on the Nuclear Magnetic Resonance (NMR) parameters of hydrogen-bonded clusters of glycine molecules in gas-phase. DFT predicted isotropic chemical shifts of H, C, N and O of the isolated glycine with respect to standard reference materials are in reasonable agreement with available experimental data. The variations of isotropic and anisotropic chemical shifts for all atoms constituting these clusters containing up to four glycine molecules have been investigated systematically employing gradient corrected hybrid B3LYP functional with three different types of extended basis sets. The clusters are mainly stabilized by a network of strong hydrogen bonds among the carboxylic (COOH) groups of glycine monomers. The formation of hydrogen bond influences the molecular structure of the clusters significantly which, on the other hand, gets reflected in the variations of NMR properties. The carbon (C) atom of the sbnd COOH group, the bridging hydrogen (H) and the proton-donor oxygen (O) atom of the Osbnd H bond suffer downfield shift due to the formation of hydrogen bond. The hydrogen bond lengths and the structural complexity of the clusters are found to vary with the number of participating monomers. A direct correlation between the hydrogen bond length and isotropic chemical shift of the bridging hydrogen is observed in all cases. The individual variations of the principal axis elements in chemical shift tensor provide additional insight about the different nature of the monomers within the cluster.

  17. Influence of gas-phase reactions on the product yields obtained in the pyrolysis of polyethylene

    Energy Technology Data Exchange (ETDEWEB)

    Cozzani, V.; Tognotti, L. [Univ. degli Studi di Pisa (Italy); Nicolella, C.; Rovatti, M. [Univ. degli Studi di Genova (Italy). Ist. di Ingegneria Chimica e di Processo G.B. Bonino

    1997-02-01

    The amount of plastic wastes is growing year after year, and the fraction of plastics in municipal solid wastes (MSW) and in refuse-derived fuels (RDF) is progressively increasing. Pyrolysis and gasification processes appear to be promising routes for the upgrading of solid wastes to more usable and energy dense materials such as gas fuel and/or fuel oil or to high-value feedstocks for the chemical industry. The characterization of the product fractions obtained from the pyrolysis of polyethylene (PE) in a laboratory-scale fixed bed reactor was performed. The experimental system allowed quantitative information to be obtained on the global tar, char, and gas yields. Pyrolysis runs were performed using reactor temperatures ranging between 500 and 800 C. The influence of the residence times in the reactor of the primary volatiles generated by the pyrolysis process was also discussed. The secondary reactivity of the tar originated from PE pyrolysis was examined. A lumped-parameters approach was used in order to evaluate the global kinetic parameters for the gas-phase tar-cracking process. PE tars resulted to be more refractory to thermal decomposition than those obtained in the pyrolysis of biomass and lignocellulosic materials, but more reactive than tars obtained in the pyrolysis of coal.

  18. Secondary Organic Aerosol formation from the gas-phase reaction of catechol with ozone

    Science.gov (United States)

    Coeur-Tourneur, C.; Tomas, A.; Guilloteau, A.; Henry, F.; Ledoux, F.; Visez, N.; Riffault, V.; Wenger, J. C.; Bedjanian, Y.; Foulon, V.

    2009-04-01

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers (at the LPCA in France and at the CRAC in Ireland). Aerosol production was monitored using a scanning mobility particle sizer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (Mo) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm-3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The aerosol yields determined in the LPCA and CRAC smog chambers were comparable and were also in accordance with those determined in a previous study performed in EUPHORE (EUropean PHOto REactor, Spain).

  19. Flame Retardancy of Sorbitol Based Bioepoxy via Combined Solid and Gas Phase Action

    Directory of Open Access Journals (Sweden)

    Beáta Szolnoki

    2016-08-01

    Full Text Available Flame-retarded bioepoxy resins were prepared with the application of commercially available sorbitol polyglycidyl ether (SPE. The additive-type flame retardancy of the cycloaliphatic amine-cured SPE was investigated. Three-percent phosphorus (P-containing samples were prepared with the application of the liquid resorcinol bis(diphenyl phosphate (RDP, the solid ammonium polyphosphate (APP, and by combining them. Synergistic effect was found between the inorganic APP and the organophosphorus RDP, when applied in combination: formulations applying RDP or APP alone showed increased limiting oxygen index (LOI values, however, their UL-94 standard ratings remained HB. When the same amount of P originated from the two additives, V-0, self-extinguishing rating and LOI value of 34% (v/v was reached. By the combined approach the heat release rate of SPE could be lowered by approximately 60%. The assumed balanced solid and gas phase mechanism was confirmed by thermogravimetric analysis, Fourier transform infrared spectrometry (FTIR analysis (of the gases formed during laser pyrolysis, attenuated total reflection-infrared spectrometry (ATR-IR analysis (of the charred residues, as well as by mechanical testing (of the char obtained after combustion.

  20. Decomposition of gas-phase diphenylether at 473 K by electron beam generated plasma

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hyun-Ha [Institute for Environmental Management Technology, National Institute of Advanced Industrial Science and Technology (AIST), AIST Tsukuba West, 16-1 Onogawa, Tsukuba, Ibaraki 305-8569 (Japan); Hakoda, Teruyuki [Department of Material Development, Takasaki Radiation Chemistry Research Establishment, Japan Atomic Energy Research Institute (JAERI), 1233 Watanuki, Takasaki, Gunma 370-1292 (Japan); Kojima, Takuji [Department of Material Development, Takasaki Radiation Chemistry Research Establishment, Japan Atomic Energy Research Institute (JAERI), 1233 Watanuki, Takasaki, Gunma 370-1292 (Japan)

    2003-03-07

    Decomposition of gas-phase diphenylether (DPE) in the order of several parts per million by volume (ppmv) was studied as a model compound of dioxin using a flow-type electron-beam reactor at an elevated temperature of 473 K. The ground state oxygen ({sup 3}P) atoms played an important role in the decomposition of DPE resulting in the formation of 1,4-hydroquinone (HQ) as a major ring retaining product. The high yield of hydroquinone indicated that the breakage of ether bond (C-O) is important in the initial step of DPE decomposition. Ring cleavage products were CO and CO{sub 2}, and NO{sub 2} was also produced from background N{sub 2}-O{sub 2}. The sum of the yields of HQ, CO{sub 2} and CO accounts for over 90% of the removed DPE. Hydroxyl radicals (OH) were less important in the dilute DPE decomposition at a high water content, and were mostly consumed by recombination reactions to form hydrogen peroxide. The smaller the initial DPE concentrations, the higher the decomposition efficiency and the lower the yields of primary products. NO scavenges oxygen atoms and decreases the DPE decomposition, while the addition of n-butane causes positive effect on the decomposition of DPE due to the several secondary radicals (HO{sub 2}, alkyl and alkoxy radicals) produced during the decomposition of n-butane.